MAI MULTE A MINHA CUI ON TO A M AN UNITI€¦ · Parcero E et al . , “ Phosphonated and sulfonated polyphenylsulfone membranes for fuel cell application , ” J . Membr . Sci

MAI MULTE A MINHA CUI ON TO A M AN UNITI US010053534B2

( 12 ) United States Patent Fujimoto

( 10 ) Patent No . : US 10 , 053 , 534 B2 ( 45 ) Date of Patent : Aug . 21 , 2018

( 54 ) FUNCTIONALIZATION OF DIELS - ALDER POLYPHENYLENE POLYMERS

( 58 ) Field of Classification Search CPC . . . . . . . . . . C08G 18 / 0828 ; C08G 2261 / 516 ; C08G

2261 / 1452 ; COSG 2261 / 722 ; HO1B 1 / 122 ; HO1M 8 / 1025

See application file for complete search history . ( 71 ) Applicant : National Technology & Engineering

Solutions of Sandia , LLC , Albuquerque , NM ( US )

( 56 ) References Cited ( 72 ) Inventor : Cy Fujimoto , Albuquerque , NM ( US ) U . S . PATENT DOCUMENTS

( 73 ) Assignee : National Technology & Engineering Solutions of Sandia , LLC , Albuquerque , NM ( US )

( * ) Notice : Subject to any disclaimer , the term of this patent is extended or adjusted under 35 U . S . C . 154 ( b ) by 0 days .

7 , 022 , 810 B14 / 2006 Cornelius 7 , 301 , 002 B1 11 / 2007 Cornelius et al . 7 , 582 , 683 B29 / 2009 Pivovar et al . 7 , 781 , 625 B2 8 / 2010 Earle et al . 7 , 816 , 482 B1 10 / 2010 Hibbs et al . 7 , 846 , 980 B2 12 / 2010 Pivovar et al . 7 , 875 , 101 B2 1 / 2011 Staiger et al . 7 , 888 , 397 B1 2 / 2011 Hibbs et al . 8 , 110 , 636 B1 2 / 2012 Fujimoto et al . 8 , 227 , 147 B2 7 / 2012 Kim et al . 8 , 492 , 049 B2 7 / 2013 Kim et al . 8 , 530 , 109 B2 9 / 2013 Kim et al . 8 , 809 , 483 B1 8 / 2014 Hibbs

( Continued )

( 21 ) Appl . No . : 15 / 398 , 545 ( 22 ) Filed : Jan . 4 , 2017

( 65 ) Prior Publication Data US 2017 / 0190830 A1 Jul . 6 , 2017

Related U . S . Application Data ( 60 ) Provisional application No . 62 / 274 , 569 , filed on Jan .

4 , 2016 .

OTHER PUBLICATIONS Shifrina et al . Macromolecules , 33 , 3525 - 3529 , 2000 . *

( Continued )

( 51 ) Primary Examiner — Shane Fang ( 74 ) Attorney , Agent , or Firm — Helen S . Baca

( 52 )

Int . CI . B01J 49 / 00 ( 2017 . 01 ) C08G 61 / 10 ( 2006 . 01 ) C08L 65 / 00 ( 2006 . 01 ) U . S . CI . ??? C08G 61 / 10 ( 2013 . 01 ) ; C08L 65 / 00

( 2013 . 01 ) ; C08G 2261 / 11 ( 2013 . 01 ) ; C08G 2261 / 146 ( 2013 . 01 ) ; C08G 2261 / 148

( 2013 . 01 ) ; C08G 2261 / 312 ( 2013 . 01 ) ; C08G 2261 / 46 ( 2013 . 01 ) ; C08G 2261 / 516 ( 2013 . 01 ) ;

CO8G 2261 / 72 ( 2013 . 01 ) ; C08G 2261 / 722 ( 2013 . 01 ) ; CO8G 2261 / 728 ( 2013 . 01 )

( 57 ) ABSTRACT The present invention relates to functionalized polymers including a poly ( phenylene ) structure . The structure can include any useful modifications , such as the inclusion of one or more reactive handles having an aryl group . Methods and uses of such structures and polymers are also described herein .

23 Claims , 17 Drawing Sheets

( RM ( RM ) ( RM ) ( RO ) ( RM ( RH ) ( RH ) ( RH ) n

( R3 ) , ( R ) ( R ) s ( 29 ) Rob ( R ) + RH ( reactive handle ) ( R )

. AMM ( R A ( R ) Arany R W AM ] LR )

( R ( R58 " > * 1894

- m I m ( R ) | ( R ) ( RM ) ( 11 )

US 10 , 053 , 534 B2 Page 2

( 56 ) References Cited

U . S . PATENT DOCUMENTS 9 , 048 , 480 B2 6 / 2015 Kim et al . 9 , 051 , 431 B2 6 / 2015 Kim et al . 9 , 580 , 541 B1 2 / 2017 Fujimoto et al .

2009 / 0264544 A1 * 10 / 2009 Loy C08G 61 / 02 521 / 27

2011 / 0237789 AL 2012 / 0225371 AL 2015 / 0349269 Al 2017 / 0190831 A1

9 / 2011 Weber et al . 9 / 2012 Kim et al .

12 / 2015 Lee et al . 7 / 2017 Kim et al .

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Lee KS et al . , “ An operationally flexible fuel cell based on quater nary ammonium - biphosphate ion pairs , ” Nature Energy 2016 ; 2 : art . No . 16120 ( 7 pp . ) . Lee KS et al . , “ Resonance - stabilized guanidinium - tethered poly ( phenylene ) s , " PRIME 2016 / 230th ECS Meeting held on Oct . 2 , 2016 - Oct . 7 , 2016 in Honolulu , HI ( MA2016 - 02 ) , abstract No . 2572 ( 1 p . ) . Li N et al . , “ Polymer electrolyte membranes derived from new sulfone monomers with pendent sulfonic acid groups , " Macromol ecules 2010 ; 43 : 9810 - 20 . Lim Y et al . , “ Synthesis and properties of sulfonated poly ( phenylene sulfone ) s without ether linkage by Diels - Alder reaction for PEMFC application , ” Electrochim . Acta 2014 ; 119 : 16 - 23 . Luo K et al . , “ Investigation of ionic conductivity , uptake and cation diffusion of perfluorsulfonate and sulfonated block copolymer ion exchange membrane in non - aqueous solvents , ” 231st ECS Meeting held on May 28 , 2017 - Jun . 1 , 2017 in New Orleans , LA ( MA2017 01 ) , abstract No . 166 ( 2 pp . ) . Maalouf M et al . , “ Factors enabling high mobility of protons and water in perfluorosulfonate membranes under low hydration con ditions , ” Int ' l J . Hydrogen Energy 2014 ; 39 : 2795 - 800 . Maurya S et al . , “ Importance of resonance structure on alkaline stability , " 231st ECS Meeting held on May 28 , 2017 - Jun . 1 , 2017 in New Orleans , LA ( MA2017 - 01 ) , abstract No . 1456 ( 1 p . ) . Merle G et al . , “ Anion exchange membranes for alkaline fuel cells : A review , " J . Membrane Sci . 2011 ; 377 : 1 - 35 . Mohanty AD et al . , “ Stable elastomeric anion exchange membranes based on quaternary ammonium - tethered polystyrene - b - poly ( ethyl ene - cobutylene ) - b - polystyrene triblock copolymers , " Macromol ecules 2015 ; 48 : 7085 - 95 . Murthy JK et al . , “ Aluminum chloride as a solid is not a strong Lewis acid , ” J . Phys . Chem . B 2006 ; 110 : 8314 - 9 . Noji M et al . , " Secondary benzylation using benzyl alcohols cata lyzed by lanthanoid , scandium , and hafnium triflate , " J . Org . Chem . 2003 : 68 : 9340 - 7 . Parcero E et al . , “ Phosphonated and sulfonated polyphenylsulfone membranes for fuel cell application , ” J . Membr . Sci . 2006 ; 285 : 206 13 . Poppe D et al . , " Carboxylated and sulfonated poly ( arylene - co arylene sulfone ) s : thermostable polyelectrolytes for fuel cell appli cations , ” Macromolecules 2002 ; 35 : 7936 - 41 . Rakita PE , “ Triflic acid and its derivatives : a family of useful reagents for synthesis , ” Chem . Today May Apr . 2004 : 48 - 50 . Shainyan BA et al . , “ Trifluoromethanesulfonamides and related compounds , ” Chem . Rev . 2013 ; 113 : 699 - 733 . Singh RP et al . , “ An efficient method for aromatic Friedel - Crafts alkylation , acylation , benzoylation , and sulfonylation reactions , " Tetrahedron 2001 ; 57 : 241 - 7 . Skalski TJG et al . , “ Structurally - defined , sulfo - phenylated , oligophenylenes and polyphenylenes , " J . Am Chem . Soc . 2015 ; 137 ( 38 ) : 12223 - 6 . Stanis RJ et al . , “ Evaluation of hydrogen and methanol fuel cell performance of sulfonated diels alder poly ( phenylene ) membranes , " J . Power Sci . 2010 ; 195 : 104 - 10 . Sun C - N et al . , “ Evaluation of Diels - Alder poly ( phenylene ) anion exchange membranes in all - vanadium redox flow batteries , ” Electrochem . Commun . 2014 ; 43 : 63 - 6 . Tang Z et al . , “ Block copolymer SDAPP membranes for vanadium redox flow batteries — strategy to address transport and durability , " PRIME 2016 / 230th ECS Meeting held on Oct . 2 , 2016 - Oct . 7 , 2016 in Honolulu , HI ( MA2016 - 02 ) , abstract No . 19 ( 2 pp . ) . International Search Report ( Form PCT / ISA / 210 ) , for International application No . PCT / US17 / 12206 ( filing date Jan . 4 , 2017 ) , dated Apr . 13 , 2017 ( 2 pp . ) . Written Opinion of the International Searching Authority ( Form PCT / ISA / 237 ) , for International application No . PCT / US17 / 12206 ( filing date Jan . 4 , 2017 ) , dated Apr . 13 , 2017 ( 10 pp . ) .

* cited by examiner

nt Aug . 21 , 2018 Sheet 1 of 17 US 10 , 053 , 534 B2 anos com com uma ( RM ) ( RM )

( Rh ( R ) ( R ' ) , ( RF ) . AMAT

Lila ( R3 WYR ( R ) ( R ) ( RM ) TER ) ( R3 ) L

+ RH ( reactive handle ) Arun KOREYA ( R ' ) Art irla ( R3 ) , R )

m ? { R " h ( R ) , ( RM ) ( 11 )

FIG . 1

( RM ) ( AP ) in ( R ) ( RM )

( RH ) ( RM ) ( RA ) ( RH ) { R } { ( Rºh Alan Allah

( R? ) ( R3 ) - K DLR ) ( Rak READ MORE ( R3 ) , ( + 1 ) AROME

( RP

IR ' la ( R ? ! ( R ) AVERBAL ( R ) & R ( R3 ) ( R " ) ( R ' ) . ( R " ,

( RM ) ( lla )

( RM ) ( llb )

{ R } ( RM ) ( RT ) ( RM ) ( Rhin ( ( RM ) ( RA ' in

( R3 ( R ) ( R % } ( R3 ) , hla ( R ) ( RS ) L - = { R = { R ) =

( R ) oth ( RA )

ROLE ( RM ) PRO ( R ) ( RT ) FROM

dm 2018 ( Rtyn ( RM ) in

( Ild ) ( llc ) FIG . 2A

U . S . Patent Aug . 21 , 2018 Sheet 2 of 17 US 10 , 053 , 534 B2

( RM ) ( RH ) ( RA ) ( RM

- - - - ( R )

( R ' ) ( R ' ) = ( R ) ( R3 ) R ( RA ) ( R3 )

im ( RH ) ( Ile ) ( Ilf )

( RM ) ( RH ) n h

( RH

( RH ) ( lig )

( RH ) ( lih )

( R " ) n ( RM )

( RM ) An ( R ' ( RM ) ( RH )

la ( R ' ) ( R ' ) ( RH )

( RHM Arlott ! Ar } } wwwwww

ArM 7

( R ' ) ( R ' ) , ( RM ) ( III )

TRATA ( R h ( R ) h

( Lj )

FIG . 2B

U . S . Patente e un no sman U . S . Patent Aug . 21 , 2018 Sheet 3 of 17 US 10 , 053 , 534 B2

( RA ) ( RH )

( * ) ( * * ) Rºn

( RM ) M

RE ( R1 ) reactive end group ( R3 ) 1

Aila Ana 9 ( RO ) S RL

( R * ) ( R ' m sublink reactive end group

( RM ) ( III ) ( 11 )

( RH ) ( RM )

( RM ) ( RH ) ( RM ) ARI

( RA ) ( R ) ( RM ) ( R3 ( R3 ) ? ( R ) a = < ( RM ) ( RH ) ( RH ) ( RF ) , ( RA ) ( R3 ) Army ( R ) ( R4 ) TY ( R ) ( R ' ) Any

< Relayu yapma { R } , { R } h Im

( RM )

( R ) ( R3 ) reactive end group

( R ) ( R ) ( Illa ) ( RO )

V R ! y { R3 ) 94

( Rhon ( RMIR ( RA )

reactive end group

sublink

FIG . 3A


( RM ) ( RM ) ( RM ) Play o Jalan ( RAM

nly ( R $ ( R ) ( R )

( R3 PM

( RU ) R ( R3 kape reactive end group ( RP

( RF ) ( RF ) ( R ) ( R ' ) , ARY

( R ) , ANO RA ( Roja ( RO ( Rºh Arhux

( R R ) CRM ) ( R ) & b rand

CRMA ( RM ) ( III )

reactive end group

sublink

( RM ) ( RM )

( RFID ( RA ) ( RM ) ( RT )

ALL WR ) * ERS ( ) ( AH )

( RA ( RH )

L RHIN ( R3 )

( RAY ( RO ) med ( RB )

( R ) a Åla Art ( R2 )

( Ryn ( BP . ( RM )

EKR ) ( R3 ) am Arl reactive

end group

( Illc )

( R ' ) ( R A T AMIA KIRQ ( Aza

{ R } } h ( Rºh . reactive ( RA ) end group

sublink

FIG . 3B


( RH ) ( RH ) ! ( R ( RA ) Ah 7777

( R ) ( RM ) ( RM )

( ( RM ) l AX

( RS ) AR ( Rhin alo

( RM ) na Ar ( Rºh 1 [ R ' ( R ?

LE ( RM ) reactive

end group ( RH ) in ( R ) ( R " ) THE

( IIld ) ( R2 ) . to on erine ( RF ) ( RF ) h vatele reactive end group

sublink

FIG . 3C

H1 8888 ha RHI

( RMX )

A19 : 11 larid

LA F - labeled DAPP an

RH RH1

( I - 1 )

FIG . 4A

som - - - . U . S . Patent Aug . 21 , 2018 Sheet 6 of 17 US 10 , 053 , 534 B2

RH

RHI ( RH - X )

viimeinen

DAPP

RHI ( 11 - 2 )

FIG . 4B

RHI RHI QH1

D

H2SO4

in m

00 ( 13 ) ( 1 - 3 ) ( 114 )

RHI RH1 RHI RHI FIG . 4C


RAN RHt RHT RHI RH RH1 RHI RORAILERHY

oshi Ousmane RH1 RH ? berano RMER

RH1 ( RH - X )

are vere

DAPP

RHII VRH

RH1 RH1 ( 11 - 5 )

FIG . 5A

RH RHI

RHI RHI RHYRH ?

phic VRH R ' R ' Rhi ,

RHI . . SO2 - X Rhi R 1

( R - X }

SO , RHI

I lay pain - -

DAPP RHI SO2 RHI . nl ! Vam ph1

RHO PRIES ( 11 - 6 )

FIG . 5B

atent Aug . 21 , 2018 Sheet 8 of 17 US 10 , 053 , 534 B2

| ( R7h ( RM ) PM ( RF ) ; R ) ( IV )

( R217 ( R )

Lewen Arb ( R ) ( R9 ) a = - ( R )

( RH ) ( Rhin . . . e it . . . V RDA APART

> ROMA Harta ( RM ) { R " } , linking second

segment segment The woment e un secondo first segment

FIG . 6A

( RM ) ( RM ) ( Ryn ( R ( RM ) ( RM )

) ( R ) , ( R3 ) Ll ( R ) = { R3 ) RS ( R ) ( RH ) n ( RH ) n .

RL VaR ) AMMO end group ( R ) a ty ja reactive Tata Re Am www am ( R " h ( R " } ,

( RM ) w

inking second reactive segment segment end group

first segment

FIG . 6B

( RA ) ( RA ) ( RA ) n

( RH ) ( RA ) ( RH ) For the va ( Va )

( R ) ( R ) - K ( RA )

( RM ) ( RH ) hi Ari { R } ( R ) ( R )

( R ) , ( R3 ) ( R4 ) n ( RM )

( RH )

TAL Crivivivivvvvv reactive end group and m7

linking second segment segment

reactive end group first segment first segment

FIG . 6C


( RM ) ( RH )

( R * * ) ( RR ) ( RH ) ( RH ) *

( R ) ( RA )

TRATA ( RM ( RT ) ( RMyn Alloh Alo

( RDS WR ) , = - ( Rº ) ( R3L Hy + RA ( functional group ) ( R3

( RH } . . . Arhii As ( R " ( R ) . AM 7 [ { R ' )

( RO ) ( RM )

( R ' ) ? ( R )

( RM ) ( RA ) ( II )

{ R % ) Tay la ( RH ( RH )

( RH ) ma ( VI )

- { R } * ) * - PRH ' - RA ) a and - ( RH ) n - a , where ach

FIG . 7

$ O9H 9O3H ?O2H SOZH $ 03H 9O3H ?OgH ?Ogh

SO3H SO3H

SOCH SO3H only pendent positions sulfonated

in SDAPP polymer

SOSH SOH both pendent and backbone positions sulfonated , providing fully - sulfonated SDAPP ( FS - SDAPP )

?O3H ?O2H ?O2H SOH ?OgH ?OgH ?OH 9O3H

HO2S H038 SOH SOgH

SOSH SOZH reactive groups with pendent positions sulfonated

in SOAPP polymer

FIG , SA

SO3H SO3H reactive groups

in FS - SDAPP polymer


Arty Akty w I

Arh Rosy LAKH AKH th

( R3 ) , pla 23 ( R ) s ( R ( RO ) . She Apho ( LH - Anty ) A ( CH - Aky ) ,

R ) Anthony ( R3 , ( R ) . ( R ) ( R3 )

( R ' ) & ( R )

= ( R " ) AND ROM > ( R )

LiH I ' S m - Arty AK

wa

Ak

( TIK ) ( II )

Art ALM h th

( R % , ( R ) , DR ) ROR ) , A . 11 AM 7 ( R ' ) A ( RP )

( R ) ( R ) , La ( RO ) A V Rhe Jin

framebord Ary ( Airey en ( Ilm ) ( In )

Arty . H ih

( R % } sa ( R ) ( RO ) ? ( R ) - - ( R°g ( R3 - ( R ) , - Apky

A3 ( R ) ( Rha ( R3 ) .

( R ) Arm7 ( R ) I ( RO ) ( R3 )

win Arty Akt ) ( llo ) ( llo )

FIG . 8B


RH1

RHIT 247 RHI SH RHI R477 RHI ha

( R ) ( R ) ( R3 ) ( R

LA ( R3 ) ( R ' ) a ????????????????????????????????????????????? ( R3 ) . > ( R ) ( R ( R ) . AMM7 ( RP ) . )

16 m ( R3 Format ( R3 ) RHI RHO MY

1 HRM RHI V RH1 RH1 R1 / h1 RH

( Ilg ) ( lir )

FIG . 8C


( 11 - 7 ) ( 11 - 8 )

De som en lang reny per are they Ar101

( 11 - 9 ) ( 11 - 10 )

0 0 lib

kelin IV F

Hinnon llar10 Karlo -

( I1 - 11 ) ( 11 - 12 )

FIG . 9


AICH

de www

DAPP ad m

alkyl acylated DAPP

FIG . 10A

05 insoluble product

AICI :

AGOTE

DAPP

aryloylated DAPP

FIG . 10B


AGCI - ? ???? ????? or

??? 4 TO ?

FIG . 10C

4 eq .

4 eg , AaQTf it DCE

?? ??????? ?????

. ??????????????????? ?? F - labeled Dapp

( 11 . 13 ) F

FIG . 11A


NNY + + + - - - - - - - - - - - - - - -

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issimi . .

4 : 22 . * * *

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FIG . 11B

OCH3

Hoo - ocha K2CO3

( 11 - 13 ) F ( 11 - 143 b locha FIG . 11C


SO ,

CUS O = 0 = 0

M ( OT )

F - labeled DAPP 1m

( 11 - 15 )

FIG . 12

og ( 2 * )

F - labeled DAPP ( 34 )

AgoTf in DCE

m

( I1 - 16 )

FIG . 13


NMe3 AK

SO3H Bolalo 8CM @ CEOs 1024 ( 11 - 17 )

FIG . 14

US 10 , 053 , 534 B2 FUNCTIONALIZATION OF DIELS - ALDER

POLYPHENYLENE POLYMERS ( II )

( RH ) ( R ) ( RH ) ( RH ) in ( RM ) n ( RH CROSS - REFERENCE TO RELATED

APPLICATION 5

( R3 _ | | SR ) , This application claims the benefit of U . S . Provisional Application No . 62 / 274 , 569 , filed Jan . 4 , 2016 , which is hereby incorporated by reference in its entirety . 10 Ar > ( R )

AM STATEMENT OF GOVERNMENT INTEREST ( R )

L A ( R ' ) q

This invention was made with Government support under 15 contract no . DE - AC04 - 94AL85000 awarded by the U . S . Department of Energy to Sandia Corporation . The Govern ( R " h ( Rºn ( RH ) , ment has certain rights in the invention .

or a salt thereof ( e . g . , a cationic salt , such as a sodium salt , FIELD OF THE INVENTION or a form thereof including a counter ion , such as a hydrox

ide ) . In some embodiments , each RH is , independently , H , The present invention relates to functionalized polymers optionally substituted alkyl ( e . g . , C1 - 12 alkyl ) , optionally including a poly ( phenylene ) structure . The structure can 25 substituted haloalkyl ( e . g . , C1 - 12 haloalkyl ) , optionally sub include any useful modifications , such as the inclusion of - - stituted perfluoroalkyl ( e . g . , C1 - 12 perfluoroalkyl ) , optionally one or more reactive handles having an aryl group . Methods substituted heteroalkyl ( e . g . , C1 - 12 heteroalkyl ) , halo , and uses of such structures and polymers are also described optionally substituted aryl ( e . g . , C4 - 18 aryl ) , optionally sub herein . stituted alkaryl ( e . g . , C1 - 12 alk - C4 - 18 aryl or C1 - 6 alk - C4 - 18

30 aryl ) , optionally substituted arylalkoxy ( e . g . , C4 - 18 aryl BACKGROUND OF THE INVENTION C1 - 12 alkoxy or C4 - 18 aryl - C1 - 6 alkoxy ) , optionally substi

tuted aryloxy ( e . g . , C4 - 18 aryloxy ) , optionally substituted aryloxycarbonyl ( e . g . , C5 - 19 aryloxycarbonyl ) , optionally Polymers including a poly ( phenylene ) backbone can pro substituted aryloyl ( e . g . , C7 - 11 aryloyl or C5 - 19 aryloyl ) , vide improved properties , including enhanced chemical sta cat sa 35 optionally substituted arylcarbonylalkyl ( e . g . , C4 - 18 arylcar bility and / or strength . Thus , such robust polymers have been bonyl - C1 - 12 alkyl or C4 - 18 arylcarbonyl - C1 - 6 alkyl ) , option

examined for use in fuel battery cells . However , further ally substituted arvlsulfonyl ( e . g . , C . arylsulfoyl ) , or chemical functionalities are desired to increase performance , optionally substituted arylsulfonylalkyl ( e . g . , C218 arylsul such as tunable conductivity , hydrophobicity , hydrophilicity , fonyl - C , , , alkyl or Clearylsulfonyl - C , alkyl ) . and / or electrochemistry . If possible , synthetic methods to 40 In some embodiments , each Rl or R3 is , independently , H , instill those chemical functionalities would maintain the optionally substituted C1 - 12 alkyl , optionally substituted durability provided by the backbone , while also providing C1 - 12 haloalkyl , optionally substituted C1 - 12 perfluoroalkyl , tunability of its chemical properties . Additional starting optionally substituted C1 - 12 heteroalkyl , RS , RP , Rº , or RF , materials , compositions , and methods to address such con where RS is an acidic moiety including a sulfonyl group , RP cerns are desired . 45 is an acidic moiety including a phosphoryl group , Rº is an

acidic moiety including a carbonyl group , and R * is an electron - withdrawing moiety ; each Ar is , independently , a

SUMMARY OF THE INVENTION bivalent linker including optionally substituted arylene ; each Am is , independently , a bivalent linker including optionally

The present invention relates to polymer compounds and 50 substituted arylene ; each q is , independently , an integer of compositions having a poly ( phenylene ) structure in combi - from 0 to 5 ( e . g . , where each q for R is , independently , 0 or nation with one or more reactive handles that can be used to 1 ) ; each h is , independently , an integer of from 0 to 5 , impart other chemical functionalities . In one instance , the wherein at least one h is not 0 ; and m is an integer of from reactive handle can be instilled on the composition ( e . g . , a about 1 to 1000 ( e . g . , from about 1 to 500 ) . In further side chain of the polymer ) , and then further functional 55 embodiments , at least one R or Are in formula ( II ) includes groups can be bonded to the reactive handle in order to RS , RP , RC , or RF . In some embodiments , q for R ' is 1 . In provide one or more tunable chemical characteristics . other embodiments , at least one RH includes an optionally Indeed , the reactive handle can be employed to provide any substituted aryl group . In some embodiments , h for Art is an

integer of from 0 to 5 ; and / or h for all other aryl groups is useful functional group in a controlled manner . In this way , 60 an integer of from 1 to 5 . In some embodiments , each and the poly ( phenylene ) backbone imparts durability to the every R3 is , independently , RH , RS , RP , RC , or RF . polymer , whereas the reactive handle provides an orthogo In some embodiments , RH is - LH _ ATH . In other embodi nal , synthetic avenue to instill useful chemical moieties . ments , RH is - LH - AKH . In one instance , ApH is an optionally

Accordingly , in one aspect , the present invention features substituted aryl ( e . g . , substituted with one or more substitu a composition ( e . g . , a molecule , a monomer , a polymer , an 65 ents selected from the group of halo , cyano , optionally article , etc . ) including the formula ( II ) , having the formula substituted haloalkyl , optionally substituted perfluoroalkyl , ( II ) , or including a structure having the formula ( II ) : optionally substituted nitroalkyl , and optionally substituted

US 10 , 053 , 534 B2

( R3 )

Apl ( R RI ) )

alkyl ) . In another instance , AKA is an optionally substituted substituted C4 - 18 aryloxy ( e . g . , including one or more halo or alkyl or optionally substituted heteroalkyl ( e . g . , substituted haloalkyl ) , optionally substituted C5 - 19 aryloxycarbonyl , with one or more substituents selected from the group of optionally substituted C5 - 19 aryloyl , optionally substituted halo , cyano , optionally substituted haloalkyl , optionally Ca 18 arylcarbonyl - C1 - 6 alkyl , optionally substituted C4 - 18 substituted perfluoroalkyl , optionally substituted nitroalkyl , 5 arylsulfonyl , or optionally substituted Ca . 18 arylsulfonyl and optionally substituted alkyl ) . C1 - 6 alkyl . In some embodiments , each and every RA In one instance , LH is a covalent bond , carbonyl ( C . includes an optionally substituted aryl group . In other ( 0 ) — ) , oxy ( 0 - ) , thio ( S — ) , azo ( N = N — ) , embodiments , each and every RH is selected from the group phosphonoyl ( P ( O ) H — ) , phosphoryl ( P ( O ) < ) , sulfonyl of an optionally substituted C4 - 18 aryl , optionally substituted ( S ( 0 ) 2 – ) , sulfinyl ( S ( 0 ) — ) , sulfonamide ( e . g . , 10 - S02 — NR23 — or — NR23 _ S02 – , where R23 is H , C1 - 6 alk - C4 - 18 aryl , optionally substituted C4 - 18 aryl - C1 - 6

alkoxy , optionally substituted C4 - 18 aryloxy , optionally sub optionally substituted alkyl , optionally substituted haloalkyl , optionally substituted alkoxy , optionally substituted alkaryl , stituted C5 - 19 aryloxycarbonyl , optionally substituted C5 - 19 optionally substituted aryl , or halo ) , imino ( NH — ) , imine aryloyl , optionally substituted C4 - 18 arylcarbonyl - C1 - 6 alkyl , ( e . g . , _ CRI N — , where R2 is H or optionally substi - 15 optionally substituted C4 - 18 arylsulfonyl , and optionally sub tuted alkyl ) , phosphine ( e . g . , - PR23 — group , where R23 is stituted C4 - 18 arylsulfonyl - C1 - 6 alkyl .

In another aspect , the present invention features a com H or optionally substituted alkyl ) , nitrilo ( e . g . , NR 3 - , where R23 is H , optionally substituted alkyl , optionally position ( e . g . , a molecule , a monomer , a polymer , an article , substituted haloalkyl , optionally substituted alkoxy , option etc . ) including the formula ( III ) , having the formula ( III ) , or

including a structure having the formula ( III ) : ally substituted alkaryl , optionally substituted aryl , or halo ) , 20 optionally substituted C1 - 12 alkylene , optionally substituted C1 - 12 alkyleneoxy , optionally substituted C1 - 12 heteroalky ( III ) lene , optionally substituted C1 - 12 heteroalkyleneoxy , option ally substituted C4 - 18 arylene , or optionally substituted C4 - 18 ( RH ) n ( RH ) n ( RH ) ( RH ( RM ) n ( RH ) aryleneoxy ( e . g . , ( CR RC2 ) — , - C ( O ) NR 3 — 25 - NR23C ( O ) - , - 502 - NR23 — , - NR23 _ S02 — , — ( CRLIR 2 a - C ( O ) - NR23 — , - ( CRLIR 2 ) — NR23 _ C ( O ) - , - ( CRLIRL2 ) S0 , - NRL3 , or ( R ) - S0 , - NR23 — ( CRLIR2 ) , where each of RII , R£2 , and R23 is , independently , H , optionally substituted alkyl , 30 optionally substituted haloalkyl , optionally substituted alkoxy , optionally substituted alkaryl , optionally substituted aryl , or halo ) . L ' - R2

In other embodiments , RS is - SO2 - OH , SO2 - RSI , - RSA — S0 , RSI , S0 , RAP , RS4 — 30 , - R4r , 35 SO NRM RN2 , - N ( RNI ) SO , RS3 , SO , NRM — ( R ) JA

RS2 , or - S02 - NRM _ S02 R $ 3 ( e . g . , where each of RSI , ( RH ) ( RH ) n ( RM RS3 , RS3 , RAF , RSA , RM , and RN2 is any described herein ) . In some embodiments , Rºis — CO H , C ( O ) - RCI , or

- RCA _ C ( O ) - RC ( e . g . , where each of RC1 and RCA is any 40 or a salt thereof ( e . g . , a cationic salt , such as a sodium salt ) . described herein ) . In some embodiments , each of RH , R ' , R3 , Art , Ar , q , h ,

In some embodiments , RP is — P ( O ) ( OH ) , , O PO m , n , L ' , and R ' is , independently , any described herein . In ( OH ) , P ( O ) HRPI , P ( O ) < RPIRP2 , — P ( O ) < R4PRP2 , some embodiments , each R ' is , independently , an electro - P ( O ) < R4rR4r . - RPAP ( O ) < RPIRP2 . - RÞA _ P ( OK philic reactive end group ( e . g . , any herein , such as optionally RARP , RP4 — P ( O ) < RA ' RAY , 0 P ( O ) < RPIRÉ2 , 45 substituted C7 - 11 aryloyl or optionally substituted C6 - 18 aryl ) . - O P ( O ) < RAIRP2 , or _ 0 _ P ( OKRAIR?r ( e . g . , where In yet another aspect , the present invention features a each of RP1 , RP2 , R4r , and RPA is any described herein , and composition ( e . g . , a molecule , a monomer , a polymer , an where each R4r can be the same or different ) . article , etc . ) including the formula ( IV ) , having the formula

In some embodiments , RF is optionally substituted C7 - 11 ( IV ) , or including a structure having the formula ( IV ) : aryloyl , optionally substituted C6 - 18 aryl , carboxyaldehyde , 50 optionally substituted C2 - , alkanoyl , optionally substituted

( IV ) C1 - 12 alkyl , optionally substituted C1 - 12 haloalkyl , optionally substituted C2 - 7 alkoxycarbonyl , nitro , nitroso , cyano , sulfo , ( RH ) ( RH ) ( R ( RH ) ( RH ) ( RH ) carboxyl , and quaternary ammonium ( e . g . , any described herein ) . In other embodiments , R? includes or is substituted 55 by perfluoroalkyl ( e . g . , C1 - 12 perfluoroalkyl ) .

In some embodiments , the composition includes a struc ture having any one of formulas ( IIk ) - ( IIr ) , or a salt thereof . In other embodiments , each RH1 is , independently , selected from the group consisting of H , halo , cyano , optionally 60 substituted haloalkyl , optionally substituted perfluoroalkyl , Ar * 17 optionally substituted nitroalkyl , and optionally substituted alkyl ; and / or each hl is , independently , if present , an integer of from 1 to 12 .

In some embodiments , at least one RH is an optionally 65 ( R " A ( R " h ( R " substituted C4 - 18 aryl , optionally substituted C1 - 6 alk - C4 - 18 aryl , optionally substituted C4 - 18 aryl - C1 - 6 alkoxy , optionally

Alai lar BRE ( R3

( R ) , X - Y Rha Jan m

US 10 , 053 , 534 B2

or a salt thereof ( e . g . , a cationic salt , such as a sodium salt ) . In some embodiments , each of RA , R1 , R2 , Art , Am , q , h , m , n , L , and Ar * is , independently , any described herein . In some embodiments , each of m and n is , independently , an integer of from about 1 to 1000 ( e . g . , from about 1 to 500 ) ; 5 L is a linking segment ; and Ar * is a hydrophobic segment . In further embodiments , at least one R1 or Are in formula ( IV ) includes RH , RS , RP , RC , or RF .

In yet another aspect , the present invention features a composition ( e . g . , a molecule , a monomer , a polymer , an 10 article , etc . ) including the formula ( V ) , having the formula ( V ) , or including a structure having the formula ( V ) :

or a salt thereof ( e . g . , a cationic salt , such as a sodium salt ) . In some embodiments , each of RM , R1 , R2 , Art , Arm , q , h , m , n , L , and Ar * is , independently , any described herein . In some embodiments , each of m and n is , independently , an integer of from about 1 to 1000 ( e . g . , from about 1 to 500 ) ; L is a linking segment ; and Ar * is a hydrophobic segment . In further embodiments , at least one R or Art in formula ( Va ) includes RH , RS , RP , RC , or R . .

In yet another aspect , the present invention features a composition ( e . g . , a molecule , a monomer , a polymer , an article , etc . ) including the formula ( VI ) , having the formula ( VI ) , or including a structure having the formula ( VI ) :

( VI ) ( V ) 15 ( RH * ) # ( Rh * ) n * ( RH * ) *

( RH ( RM ) ( RH ) ( RH )

( RH ) n ) ( RH * ) # ( Rh * ) * ( RH * ) + ATT ( R ) Alah log

30 ( R3 20 ( R ) ( R ) ( RH

h LAM , R17 ( R ! ) ) ( R ' ) a L - Ar * In - RL 25 Da reacti reactive end group ( Rº ) - ( R ) ?

( R ̂ ) . ( R ̂ ) . ( RH )

Jm linking second reactive segment segment end

group ( R3 ) LE Rua -

( RH * ) * ( RH * ) n * ( RH * ) n + 30 first segment

or a salt thereof ( e . g . , a cationic salt , such as a sodium salt ) . or a salt thereof ( e . g . , a cationic salt , such as a sodium salt ) . In some embodiments , each RH * is , independently , RH or In some embodiments , each of RH , R ' , R3 , RP , Ar , ATM , q , RH — R4 , where R4 is a functional group ( e . g . , any herein , h , m , n , L , and Ar * is , independently , any described herein . 35 such as halo , cyano , nitro , nitroso , amino , amido , thio , In some embodiments , each of m and n is , independently , an optionally substituted alkyl , optionally substituted haloalkyl , integer of from about 1 to 1000 ( e . g . , from about 1 to 500 ) ; perfluoroalkyl , etc . ) . In some embodiments , each of RH , R ' , L is a linking segment ; and Ar * is a hydrophobic segment . R ” , Art , Ar , q , h * , and m is , independently , any described In further embodiments , at least one R or Art in formula ( V ) herein . In some embodiments , each h * is , independently , an includes RH , RS , RP , RC , or RF . 40 integer of from 0 to 5 , wherein at least one h * is not 0 . In

In another aspect , the present invention features a com further embodiments , at least one R ' or Ar in formula ( VI ) position ( e . g . , a molecule , a monomer , a polymer , an article , includes RH , RS , R1 , RC , or RF . etc . ) including the formula ( Va ) , having the formula ( Va ) , or In another aspect , the present invention features a method including a structure having the formula ( Va ) : ( e . g . , of forming a polymer ) , the method including providing

( Va ) ( RM ) n ( RH ) n ( RH ) n

Ala la ( RH ) n ( RH ) n ( RH ) n la

( R ) , TI ( R ' ) - - ( Rº ) a

Art . ( RM )

( Rºa | ( RH ) | ( R ) 8 1 - + Ar * In Saiu RH ,

- ( R ? ) VA = L

( RH ) n ( R ) ( RM )

( R3 ) linking second segment segment

reactive end group - reactive

end group

first segment

US 10 , 053 , 534 B2

a first composition including a structure having the formula Definitions ( I ) ( e . g . , any described herein ) and reacting the first com As used herein , the term “ about ” means + / - 10 % of any position with a reagent having the structure RH — X in the recited value . As used herein , this term modifies any recited presence of a metal catalyst , where X is a leaving group and value , range of values , or endpoints of one or more ranges . R “ comprises an optionally substituted aryl group . In some 5 The term “ acyl , ” or “ alkanoyl , ” as used interchangeably embodiments , the method thereby produces a second com herein , represent an alkyl group , as defined herein , or position including a structure having the formula ( II ) and hydrogen attached to the parent molecular group through a further including one or more RH covalently bonded to one carbonyl group , as defined herein . This group is exemplified or more aryl rings in the structure . In further embodiments , by formyl , acetyl , propionyl , butanoyl , and the like . The the second composition is a composition including a struc - 10 alkanoyl group can be substituted or unsubstituted . For ture having the formula ( I ) , ( II ) , ( III ) , ( IV ) , ( V ) , or ( VI ) , or example , the alkanoyl group can be substituted with one or a salt thereof .

In some embodiments , X is halo . In other embodiments , more substitution groups , as described herein for alkyl . In RH is any described herein ( e . g . , optionally substituted aryl , some embodiments , the unsubstituted acyl group is a C2 - 7 optionally substituted alkaryl , optionally substituted arylal - 15 acyl or alkanoyl group . koxy , optionally substituted aryloxy , optionally substituted By “ alkaryl ” is meant an aryl group , as defined herein , aryloxycarbonyl , optionally substituted aryloyl , optionally attached to the parent molecular group through an alkylene substituted arylsulfonyl , optionally substituted arylsulfonyl group , as defined herein . Similarly , by the term “ alkhet alkyl , - LH — ArH , or - I H - AKH ) . eroaryl ” is meant a heteroaryl group , as defined herein ,

In some embodiments , metal catalyst is a metal alkyl 20 attached to the parent molecular group through an alkylene sulfate , a metal sulfoamino , a metal alkylsulfonylamide , or group . Other groups preceded by the prefix “ alk - ” are a metal alkylsulfonylalkyl . Exemplary metal catalysts defined in the same manner . The alkaryl group can be include M [ O ( SO2 RMF ) ] , M [ N ( SO2 - RMF ) 2 ] , and MC substituted or unsubstituted . For example , the alkaryl group ( S02 — RMF ) 3 ] ; where RMF is optionally substituted alkyl , can be substituted with one or more substitution groups , as optionally substituted aryl , optionally substituted alkaryl , 25 described herein for alkyl and / or aryl . Exemplary unsubsti optionally substituted haloalkyl , or perfluoroalkyl ; and tuted alkaryl groups are of from 7 to 16 carbons ( C7 - 16 where M is Ag , A1 , Ba , Bi , Ca , Cu , In , Re , Sc , Sn , Ti , Yb , alkaryl ) , as well as those having an alkylene group with 1 to or Zn . Further exemplary catalyst include AgoTf , Ag ( NTE ) , 6 carbons and an aryl group with 4 to 18 carbons ( i . e . , C1 - 6 Al ( OTf ) 3 , Al ( NTf2 ) , Bi ( OTf ) 3 , In ( OTf ) , Sn ( OTf ) 4 , alk - C4 - 18 aryl ) . Sn ( NTf24 , Ti ( OTf ) 4 , Ti ( NTf2 ) 4 , Yb ( OTf ) 3 , Yb ( NTf2 ) 3 , 30 By “ alkcycloalkyl ” is meant a cycloalkyl group , as Zn ( OTf ) 2 , or Zn ( NTf2 ) 2 , where Tf is S02CF3 . defined herein , attached to the parent molecular group

In some embodiments , the first composition is present in through an alkylene group , as defined herein . The alkcy a polymeric membrane . cloalkyl group can be substituted or unsubstituted . For

In any embodiment herein , the composition includes a example , the alkcycloalkyl group can be substituted with structure having any one of formulas ( IIa ) to ( IIj ) , ( II - 1 ) to 35 one or more substitution groups , as described herein for ( II - 18 ) , ( IIIa ) to ( IIId ) , or a salt thereof . In some embodi alkyl . ments , each RH is , independently , if present , H , halo , cyano , By " alkenyl ” is meant an optionally substituted C2 - 24 nitro , nitroso , optionally substituted haloalkyl , optionally alkyl group having one or more double bonds . The alkenyl substituted perfluoroalkyl , optionally substituted nitroalkyl , group can be cyclic ( e . g . , C3 - 24 cycloalkenyl ) or acyclic . The and optionally substituted alkyl ; n is an integer of from about 40 alkenyl group can also be substituted or unsubstituted . For 1 to 500 ; and each hl is , independently , if present , an integer example , the alkenyl group can be substituted with one or of from 1 to 12 . more substitution groups , as described herein for alkyl .

In any embodiment herein , L or L ' includes a covalent By “ alkheterocyclyl ” represents a heterocyclyl group , as bond , optionally substituted C1 - 12 alkylene , optionally sub - defined herein , attached to the parent molecular group stituted C1 - 12 alkyleneoxy , optionally substituted C1 - 12 het - 45 through an alkylene group , as defined herein . Exemplary eroalkylene , optionally substituted C1 - 12 heteroalkyleneoxy , unsubstituted alkheterocyclyl groups are of from 2 to 14 optionally substituted C218 arylene , optionally substituted carbons . C4 - 18 aryleneoxy , optionally substituted polyphenylene , or a By “ alkoxy ” is meant OR , where R is an optionally structure of formula ( II ) . In yet other embodiments , L or L substituted alkyl group , as described herein . Exemplary includes a structure of formula ( II ) and Ar * ( e . g . , any 50 alkoxy groups include methoxy , ethoxy , butoxy , triha subunits described herein for Ar * ) . loalkoxy , such as trifluoromethoxy , etc . The alkoxy group

In any embodiment herein , Ar * or L or L ' includes a can be substituted or unsubstituted . For example , the alkoxy structure of formula ( II ) , a sulfone subunit , an arylene group can be substituted with one or more substitution sulfone subunit , an ether sulfone subunit , an arylene ether groups , as described herein for alkyl . Exemplary unsubsti subunit , a perfluoroalkyl subunit , or a perfluoroalkoxy sub - 55 tuted alkoxy groups include C1 - 3 , C1 - 6 , C1 - 12 , C1 - 16 , C1 - 18 , unit . C1 - 20 , or C1 - 24 alkoxy groups .

In any embodiment herein , each of Art , ATM , and Ar * is By “ alkoxyalkyl ” is meant an alkyl group , as defined optionally substituted phenylene , optionally substituted herein , which is substituted with an alkoxy group , as defined naphthylene , optionally substituted phenanthrylene , a sul - herein . Exemplary unsubstituted alkoxyalkyl groups include fone subunit , an arylene sulfone subunit , an ether sulfone 60 between 2 to 12 carbons ( C2 - 12 alkoxyalkyl ) , as well as those subunit , an arylene ether subunit , a perfluoroalkyl subunit , a having an alkyl group with 1 to 6 carbons and an alkoxy perfluoroalkoxy subunit , or any described herein ( e . g . , any group with 1 to 6 carbons ( i . e . , C1 - 6 alkoxy - C1 - 6 alkyl ) . aryl group described herein ) . In further embodiments , the By " alkoxycarbonyl ” is meant an alkoxy group , as optional substitution is RH , RS , RP , RC , RF , or a label ( e . g . , defined herein , that is attached to the parent molecular group fluorine or another NMR detectable label ) . 65 through a carbonyl group . In some embodiments , an unsub

In any embodiment herein , m is less than n . In any stituted alkoxycarbonyl group is a C2 - 7 alkoxycarbonyl embodiment herein , m is more than n . group .

US 10 , 053 , 534 B2 10

By “ alkyl ” and the prefix “ alk ” is meant a branched or By “ alkylsulfonyl ” is meant an alkyl group , as defined unbranched saturated hydrocarbon group of 1 to 24 carbon herein , attached to the parent molecular group through an atoms , such as methyl , ethyl , n - propyl , isopropyl , n - butyl , SO2 - group . In some embodiments , the unsubstituted isobutyl , s - butyl , t - butyl , n - pentyl , isopentyl , s - pentyl , neo - alkylsulfonyl group is a C1 - 6 Or C1 - 12 alkylsulfonyl group . In pentyl , hexyl , heptyl , octyl , nonyl , decyl , dodecyl , tetrade - 5 other embodiments , the alkylsulfonyl group is SO2 - RSI , cyl , hexadecyl , eicosyl , tetracosyl , and the like . The alkyl where RS is an optionally substituted C1 - 12 alkyl ( e . g . , as group can be cyclic ( e . g . , C3 - 24 cycloalkyl ) or acyclic . The described herein , including optionally substituted C1 - 12 alkyl group can be branched or unbranched . The alkyl group haloalkyl or perfluoroalkyl ) . can also be substituted or unsubstituted . For example , the By “ alkylsulfonylalkyl ” is meant an alkyl group , as alkyl group can be substituted with one , two , three or , in the 10 defined herein , substituted by an alkylsulfonyl group . In case of alkyl groups of two carbons or more , four substitu some embodiments , the unsubstituted alkylsulfonylalkyl ents independently selected from the group consisting of : ( 1 ) group is a C2 - 12 or C2 - 24 alkylsulfonylalkyl group ( e . g . , C1 - 6 C1 - 6 alkoxy ; ( 2 ) C1 - 6 alkylsulfinyl ; ( 3 ) C1 - 6 alkylsulfonyl ; ( 4 ) alkylsulfonyl - C1 - 6 alkyl or C1 - 12 alkylsulfonyl - C1 - 12 alkyl ) . amino ; ( 5 ) aryl ; ( 6 ) arylalkoxy ; ( 7 ) aryloyl ; ( 8 ) azido ; ( 9 ) An exemplary alkylsulfonylalkyl group is - C — ( SO2 - Ak ) z , cyano ; ( 10 ) carboxyaldehyde ; ( 11 ) C3 - 8 cycloalkyl ; ( 12 ) 15 where each Ak is , independently , optionally substituted halo ; ( 13 ) heterocyclyl ; ( 14 ) heterocyclyloxy ; ( 15 ) hetero alkyl . cyclyloyl ; ( 16 ) hydroxyl ; ( 17 ) N - protected amino ; ( 18 ) nitro ; By “ alkylsulfonylamide ” is meant an amino group , as ( 19 ) oxo ; ( 20 ) C3 - 8 spirocyclyl ; ( 21 ) C1 - 6 thioalkoxy ; ( 22 ) defined herein , substituted by an alkylsulfonyl group . In thiol ; ( 23 ) — CO R4 , where R4 is selected from the group some embodiments , the unsubstituted alkylsulfonylamide consisting of ( a ) hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 aryl , and 20 group is — NRMRN2 , in which each of RM and RN2 is , ( d ) C - alk - C4 - 18 aryl ; ( 24 ) - C ( O ) NRPRC , where each of independently , H , C1 - 12 alkyl , or C1 - 24 alkylsulfonyl group RP and Rºis , independently , selected from the group con ( e . g . , C1 - 6 alkylsulfonyl or C1 - 12 alkylsulfonyl ) , where at sisting of ( a ) hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 aryl , and ( d ) least one of RM and RN2 includes a sulfonyl group . An C1 - 6 alk - C4 - 18 aryl ; ( 25 ) SO2R ” , where R ” is selected exemplary alkylsulfonylamide group is — N — ( SO2 - Ak ) 2 or from the group consisting of ( a ) C1 - 6 alkyl , ( b ) C4 - 18 aryl , 25 — N ( Ak ) ( SO2 - Ak ) , where each Ak is , independently , and ( c ) C1 - 6 alk - C4 - 18 aryl ; ( 26 ) — SO , NRERF , where each optionally substituted alkyl . of RF and R is , independently , selected from the group By “ alkynyl ” is meant an optionally substituted C2 - 24 consisting of ( a ) hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 aryl , and alkyl group having one or more triple bonds . The alkynyl ( d ) C1 - 6 alk - C4 - 18 aryl ; and ( 27 ) - NR RH , where each of group can be cyclic or acyclic and is exemplified by ethynyl , R and RH is , independently , selected from the group con - 30 1 - propynyl , and the like . The alkynyl group can also be sisting of ( a ) hydrogen , ( b ) an N - protecting group , ( c ) C1 - 6 substituted or unsubstituted . For example , the alkynyl group alkyl , ( d ) C2 - 6 alkenyl , ( e ) C2 - 6 alkynyl , ( f ) C4 - 18 aryl , ( g ) can be substituted with one or more substitution groups , as C1 - 6 alk - C4 - 18 aryl , ( h ) C3 - 8 cycloalkyl , and ( i ) C1 - 6 alk - C3 - 8 described herein for alkyl . cycloalkyl , wherein in one embodiment no two groups are By “ amidino ” is meant C ( NRN3 ) NRMRN2 , where each bound to the nitrogen atom through a carbonyl group or a 35 of RM , RN2 , and RN3 is , independently , H or optionally sulfonyl group . The alkyl group can be a primary , secondary , substituted alkyl , or RM and RN2 , taken together with the or tertiary alkyl group substituted with one or more sub nitrogen atom to which each are attached , form a heterocy stituents ( e . g . , one or more halo or alkoxy ) . In some embodi clyl group , as defined herein . ments , the unsubstituted alkyl group is a C1 - 3 , C1 - 6 , C1 - 122 By “ amido ” is meant C ( O ) NRMRN2 , where each of C - 16 , C1 - 18 , C1 - 20 , or C1 - 24 alkyl group . 40 RM and RN2 is , independently , H or optionally substituted By “ alkylene ” is meant a bivalent form of an alkyl group , alkyl , or RM and RN2 , taken together with the nitrogen atom

as described herein . Exemplary alkylene groups include to which each are attached , form a heterocyclyl group , as methylene , ethylene , propylene , butylene , etc . In some defined herein . embodiments , the alkylene group is a C1 - 3 , C1 - 6 , C1 - 12 , By “ amino " is meant - NRMRN2 , where each of RM and C1 - 16 , C1 - 18 , C1 - 20 , C1 - 24 , C2 - 3 , C2 - 6 , C2 - 12 , C2 - 16 , C2 - 18 , 45 RM2 is , independently , H or optionally substituted alkyl , or C2 - 20 , or C2 - 24 alkylene group . The alkylene group can be RM and RN2 , taken together with the nitrogen atom to which branched or unbranched . The alkylene group can also be each are attached , form a heterocyclyl group , as defined substituted or unsubstituted . For example , the alkylene herein . group can be substituted with one or more substitution By " aminoalkyl " is meant an alkyl group , as defined groups , as described herein for alkyl . 50 herein , substituted by an amino group , as defined herein . By " alkyleneoxy ” is meant an alkylene group , as defined By “ aryl ” is meant a group that contains any carbon - based

herein , attached to the parent molecular group through an aromatic group including , but not limited to , benzyl , naph oxygen atom . thalene , phenyl , biphenyl , phenoxybenzene , and the like . By “ alkylsulfate ” is meant an alkyl group , as defined The term “ aryl ” also includes " heteroaryl , ” which is defined

herein , attached to the parent molecular group through an 55 as a group that contains an aromatic group that has at least - 0 - ( SO , ) group . An exemplary alkylsulfate group is one heteroatom incorporated within the ring of the aromatic

O SO2 - Ak , where each Ak is , independently , optionally group . Examples of heteroatoms include , but are not limited substituted alkyl . to , nitrogen , oxygen , sulfur , and phosphorus . Likewise , the

By " alkylsulfinyl ” is meant an alkyl group , as defined term “ non - heteroaryl , ” which is also included in the term herein , attached to the parent molecular group through an 60 " aryl , ” defines a group that contains an aromatic group that - S ( O ) - group . In some embodiments , the unsubstituted does not contain a heteroatom . The aryl group can be alkylsulfinyl group is a Cl - or C - 12 alkylsulfinyl group . substituted or unsubstituted . The aryl group can be substi By “ alkylsulfinylalkyl ” is meant an alkyl group , as tuted with one , two , three , four , or five substituents inde

defined herein , substituted by an alkylsulfinyl group . In pendently selected from the group consisting of : ( 1 ) C1 - 6 some embodiments , the unsubstituted alkylsulfinylalkyl 65 alkanoyl ; ( 2 ) C1 - 6 alkyl ; ( 3 ) C1 - 6 alkoxy ; ( 4 ) C1 - 6 alkoxy group is a C2 - 12 or C2 - 24 alkylsulfinylalkyl group ( e . g . , C1 - 6 C1 - 6 alkyl ; ( 5 ) C1 - 6 alkylsulfinyl ; ( 6 ) C1 - 6 alkylsulfinyl - C1 - 6 alkylsulfinyl - C1 - 6 alkyl or C1 - 12 alkylsulfinyl - C1 - 12 alkyl ) . alkyl ; ( 7 ) C1 - 6 alkylsulfonyl ; ( 8 ) C1 - 6 alkylsulfonyl - C1 - 6

11

group

US 10 , 053 , 534 B2 12

alkyl ; ( 9 ) aryl ; ( 10 ) amino ; ( 11 ) C1 - 6 aminoalkyl ; ( 12 ) through a carbonyl group . In some embodiments , an unsub heteroaryl ; ( 13 ) C1 - 6 alk - C4 - 18 aryl ; ( 14 ) aryloyl ; ( 15 ) azido ; stituted aryloxycarbonyl group is a C5 - 19 aryloxycarbonyl ( 16 ) cyano ; ( 17 ) C1 - 6 azidoalkyl ; ( 18 ) carboxyaldehyde ; ( 19 ) group . carboxyaldehyde - C1 - 6 alkyl ; ( 20 ) C3 - 8 cycloalkyl ; ( 21 ) C1 - 6 By “ aryloyl ” is meant an aryl group that is attached to the alk - C3 - 8 cycloalkyl ; ( 22 ) halo ; ( 23 ) C1 - 6 haloalkyl ; ( 24 ) 5 parent molecular group through a carbonyl group . In some heterocyclyl ; ( 25 ) heterocyclyloxy ; ( 26 ) heterocyclyloyl ; embodiments , an unsubstituted aryloyl group is a C7 - 11 ( 27 ) hydroxyl ; ( 28 ) C1 - 6 hydroxyalkyl ; ( 29 ) nitro ; ( 30 ) C1 - 6 aryloyl or C5 - 19 aryloyl group . nitroalkyl ; ( 31 ) N - protected amino ; ( 32 ) N - protected amino By “ arylsulfonyl ” is meant an aryl group , as defined C1 - 6 alkyl ; ( 33 ) oxo ; ( 34 ) C1 - 6 thioalkoxy ; ( 35 ) thio - C1 - 6 herein , attached to the parent molecular group through an alkoxy - C1 - 6 alkyl ; ( 36 ) ( CH2 ) , COR , where r is an 10 S02 — group . integer of from zero to four , and R4 is selected from the By “ arylsulfonylalkyl ” is meant an alkyl group , as defined group consisting of ( a ) hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 herein , substituted by an arylsulfonyl group . In some aryl , and ( d ) C1 - 6 alk - C4 - 18 aryl ; ( 37 ) ( CH2 ) , CONRPR " , embodiments , the arylcarbonylalkyl group is Ar — SO2 - Ak - , where r is an integer of from zero to four and where each RB in which Ar is an optionally substituted aryl group and Ak and RC is independently selected from the group consisting 15 is an optionally substituted alkyl or optionally substituted of ( a ) hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 aryl , and ( d ) C1 - 6 alkylene group . In particular embodiments , the unsubsti alk - C4 - 18 aryl ; ( 38 ) ( CH2 ) , SO , Rº , where ris an integer of tuted arylsulfonylalkyl group is a C4 - 20 aryl - S02 - C1 - 12 from zero to four and where R is selected from the group alkyl group or a C4 - 12 aryl - SO2 – C1 - 6 alkyl group or a C4 - 18 consisting of ( a ) C1 - 6 alkyl , ( b ) C4 - 18 aryl , and ( c ) C1 - 6 aryl - SO2 - C1 - 6 alkyl group . alk - C4 - 18 aryl ; ( 39 ) - ( CH2 ) , SO NRER® , where r is an 20 By " azido ” is meant an - N3 group . integer of from zero to four and where each of RE and RF is , By “ azo ” is meant an - N = N — group . independently , selected from the group consisting of ( a ) By “ azidoalkyl ” is meant an azido group attached to the hydrogen , ( b ) C1 - 6 alkyl , ( c ) C4 - 18 aryl , and ( d ) C1 - 6 alk - C4 - 18 parent molecular group through an alkyl group , as defined aryl ; ( 40 ) — ( CH , ) , NR RH , where r is an integer of from herein . zero to four and where each of R and RH is , independently , 25 By “ carbonyl ” is meant a C ( 0 ) group , which can also selected from the group consisting of ( a ) hydrogen , ( b ) an be represented as > C = O . N - protecting group , ( c ) C1 - 6 alkyl , ( d ) C2 - 6 alkenyl , ( e ) C2 - 6 By “ carboxyaldehyde ” is meant a - C ( OH group . alkynyl , ( f ) C4 - 18 aryl , ( g ) C1 - 6 alk - C4 - 18 aryl , ( h ) C3 - 8 By " carboxyaldehydealkyl ” is meant a carboxyaldehyde cycloalkyl , and ( i ) C1 - 6 alk - C3 - 8 cycloalkyl , wherein in one group , as defined herein , attached to the parent molecular embodiment no two groups are bound to the nitrogen atom 30 group through an alkylene group , as defined herein . through a carbonyl group or a sulfonyl group ; ( 41 ) thiol ; ( 42 ) By " carboxyl ” is meant a — COH group . perfluoroalkyl ; ( 43 ) perfluoroalkoxy ; ( 44 ) aryloxy ; ( 45 ) By " cyano " is meant a CN group . cycloalkoxy ; ( 46 ) cycloalkylalkoxy ; and ( 47 ) arylalkoxy . In By " cycloalkyl ” is meant a monovalent saturated or particular embodiments , an unsubstituted aryl group is a unsaturated non - aromatic cyclic hydrocarbon group of from C4 - 18 , C4 - 14 , C4 - 12 , C4 - 10 , C6 - 18 , C6 - 14 , C6 - 12 , or C6 - 10 aryl 35 three to eight carbons , unless otherwise specified , and is group . exemplified by cyclopropyl , cyclobutyl , cyclopentyl , cyclo By “ arylcarbonylalkyl ” is meant an alkyl group , as hexyl , cycloheptyl , bicyclo [ 2 . 2 . 1 . ] heptyl and the like . The

defined herein , substituted by an aryloyl group , as defined cycloalkyl group can also be substituted or unsubstituted . herein . In some embodiments , the arylcarbonylalkyl group is For example , the cycloalkyl group can be substituted with Ar - C ( O ) - Ak - , in which Ar is an optionally substituted aryl 40 one or more groups including those described herein for group and Ak is an optionally substituted alkyl or optionally alkyl . substituted alkylene group . In particular embodiments , an By “ cycloalkoxy ” is meant a cycloalkyl group , as defined unsubstituted arylcarbonylalkyl group is a C4 - 20 aryl - C herein , attached to the parent molecular group through an ( 0 ) C1 - 12 alkyl group or a C4 - 12 aryl - C ( O ) C1 - 6 alkyl oxygen atom .

45 By “ dithiocarboxyamino " is meant — NRNIC ( S ) SRSI , By “ arylene ” is meant a bivalent form of an aryl group , as where each of RM and RSI is , independently , H or optionally

described herein . Exemplary arylene groups include phe - substituted alkyl , or RM1 and RSI , taken together with the nylene , naphthylene , biphenylene , triphenylene , diphenyl nitrogen atom to which each are attached , form a heterocy ether , acenaphthenylene , anthrylene , or phenanthrylene . In clyl group , as defined herein . some embodiments , the arylene group is a C4 - 18 , C4 - 14 , 50 By “ halo " is meant F , C1 , Br , or I . C4 - 12 , C4 - 10 , C6 - 18 , C6 - 14 , C6 - 12 , or C6 - 10 arylene group . The By “ haloalkyl ” is meant an alkyl group , as defined herein , arylene group can be branched or unbranched . The arylene substituted with one or more halo . group can also be substituted or unsubstituted . For example , By " heteroalkyl ” is meant an alkyl group , as defined the arylene group can be substituted with one or more herein , containing one , two , three , or four non - carbon het substitution groups , as described herein for aryl . 55 eroatoms ( e . g . , independently selected from the group con By “ aryleneoxy ” is meant an arylene group , as defined sisting of nitrogen , oxygen , phosphorous , sulfur , or halo ) .

herein , attached to the parent molecular group through an By “ heteroalkylene ” is meant a divalent form of an oxygen atom . alkylene group , as defined herein , containing one , two , By “ arylalkoxy ” is meant an alkaryl group , as defined three , or four non - carbon heteroatoms ( e . g . , independently

herein , attached to the parent molecular group through an 60 selected from the group consisting of nitrogen , oxygen , oxygen atom . phosphorous , sulfur , or halo ) .

By " aryloxy ” is meant - OR , where R is an optionally By “ heteroalkyleneoxy ” is meant a heteroalkylene group , substituted aryl group , as described herein . In some embodi - as defined herein , attached to the parent molecular group ments , an unsubstituted aryloxy group is a C4 - 18 or C6 - 18 through an oxygen atom . aryloxy group 65 By “ heteroaryl ” is meant a subset of heterocyclyl groups , By " aryloxycarbonyl ” is meant an aryloxy group , as as defined herein , which are aromatic , i . e . , they contain 4n + 2

defined herein , that is attached to the parent molecular group pi electrons within the mono - or multicyclic ring system .

US 10 , 053 , 534 B2 13 14

By " heterocyclyl ” is meant a 5 - , 6 - or 7 - membered ring , fluoroalkylene groups include , e . g . , OCF21 or unless otherwise specified , containing one , two , three , or CF20 , where f is an integer from about 1 to 5 , and 2f four non - carbon heteroatoms ( e . g . , independently selected is an integer that is 2 times f ( e . g . , difluoromethyleneoxy , from the group consisting of nitrogen , oxygen , phosphorous , tetrafluoroethyleneoxy , etc . ) . sulfur , or halo ) . The 5 - membered ring has zero to two double 5 By " perfluoroalkoxy ” is meant an alkoxy group , as bonds and the 6 - and 7 - membered rings have zero to three defined herein , having each hydrogen atom substituted with double bonds . The term " heterocycly1 ” also includes bicy - a fluorine atom . clic , tricyclic and tetracyclic groups in which any of the By “ phosphine ” is meant a - PR23 — group , where R23 is above heterocyclic rings is fused to one , two , or three rings H or optionally substituted alkyl . independently selected from the group consisting of an aryl 10 By " phosphono ” is meant a — P ( O ) ( OH ) 2 group . ring , a cyclohexane ring , a cyclohexene ring , a cyclopentane By “ phosphonoyl ” is meant a — P ( O ) H - group . ring , a cyclopentene ring , and another monocyclic hetero - By “ phosphoric ester " is meant a 0 - PO ( OH ) 2 group . cyclic ring , such as indolyl , quinolyl , isoquinolyl , tetrahy By “ phosphoryl ” is meant a — P ( O ) < group . droquinolyl , benzofuryl , benzothienyl and the like . Hetero By “ protecting group ” is meant any group intended to cyclics include thiiranyl , thietanyl , tetrahydrothienyl , 15 protect a reactive group against undesirable synthetic reac thianyl , thiepanyl , aziridinyl , azetidinyl , pyrrolidinyl , piper - tions . Commonly used protecting groups are disclosed in idinyl , azepanyl , pyrrolyl , pyrrolinyl , pyrazolyl , pyrazolinyl , “ Greene ' s Protective Groups in Organic Synthesis , ” John pyrazolidinyl , imidazolyl , imidazolinyl , imidazolidinyl , Wiley & Sons , New York , 2007 ( 4th ed . , eds . P . G . M . Wuts pyridyl , homopiperidinyl , pyrazinyl , piperazinyl , pyrimidi and T . W . Greene ) , which is incorporated herein by refer nyl , pyridazinyl , oxazolyl , oxazolidinyl , isoxazolyl , isox - 20 ence . O - protecting groups include an optionally substituted azolidiniyl , morpholinyl , thiomorpholinyl , thiazolyl , thiazo - alkyl group ( e . g . , forming an ether with reactive group O ) , lidinyl , isothiazolyl , isothiazolidinyl , indolyl , quinolinyl , such as methyl , methoxymethyl , methylthiomethyl , benzoy isoquinolinyl , benzimidazolyl , benzothiazolyl , benzox loxymethyl , t - butoxymethyl , etc . ; an optionally substituted azolyl , furyl , thienyl , thiazolidinyl , isothiazolyl , isoindazoyl , alkanoyl group ( e . g . , forming an ester with the reactive triazolyl , tetrazolyl , oxadiazolyl , uricyl , thiadiazolyl , pyrim - 25 group O ) , such as formyl , acetyl , chloroacetyl , fluoroacetyl idyl , tetrahydrofuranyl , dihydrofuranyl , tetrahydrothienyl , ( e . g . , perfluoroacetyl ) , methoxyacetyl , pivaloyl , t - buty dihydrothienyl , dihydroindolyl , tetrahydroquinolyl , tetrahy lacetyl , phenoxyacetyl , etc . ; an optionally substituted ary droisoquinolyl , pyranyl , dihydropyranyl , dithiazolyl , benzo loyl group ( e . g . , forming an ester with the reactive group O ) , furanyl , benzothienyl , and the like . such as - C ( O ) - Ar , including benzoyl ; an optionally sub By " heterocyclyloxy ” is meant a heterocyclyl group , as 30 stituted alkylsulfonyl group ( e . g . , forming an alkylsulfonate

defined herein , attached to the parent molecular group with reactive group O ) , such as S02 RSI , where RSI is through an oxygen atom . optionally substituted C1 - 12 alkyl , such as mesyl or benzyl By " heterocyclyloyl ” is meant a heterocyclyl group , as sulfonyl ; an optionally substituted arylsulfonyl group ( e . g . ,

defined herein , attached to the parent molecular group forming an arylsulfonate with reactive group O ) , such as through a carbonyl group . 35 SO2 - RS4 , where RS4 is optionally substituted C4 - 18 aryl ,

By “ hydroxyl ” is meant OH . such as tosyl or phenylsulfonyl ; an optionally substituted By “ hydroxyalkyl ” is meant an alkyl group , as defined alkoxycarbonyl or aryloxycarbonyl group ( e . g . , forming a

herein , substituted by one to three hydroxyl groups , with the carbonate with reactive group O ) , such as - C ( O ) - OR " , proviso that no more than one hydroxyl group may be where R7l is optionally substituted C1 - 12 alkyl or optionally attached to a single carbon atom of the alkyl group and is 40 substituted C4 - 18 aryl , such as methoxycarbonyl , methoxym exemplified by hydroxymethyl , dihydroxypropyl , and the ethylcarbonyl , t - butyloxycarbonyl ( Boc ) , or benzyloxycar like . bonyl ( Cbz ) ; or an optionally substituted silyl group ( e . g . , By " imine ” is meant CRUI — N — , where R21 is H or forming a silyl ether with reactive group O ) , such as

optionally substituted alkyl . Si ( R72 ) 3 , where each R12 is , independently , optionally By “ imino ” is meant — NH — . 45 substituted C - 1 , alkyl or optionally substituted C4 . 18 aryl , By “ nitrilo ” is meant - N < . Exemplary nitrilo groups such as trimethylsilyl , t - butyldimethylsilyl , or t - butyldiphe

include - NR23 — , where R23 is H , optionally substituted nylsilyl . N - protecting groups include , e . g . , formyl , acetyl , alkyl , optionally substituted haloalkyl , optionally substituted benzoyl , pivaloyl , t - butylacetyl , alanyl , phenylsulfonyl , ben alkoxy , optionally substituted alkaryl , optionally substituted zyl , Boc , and Cbz . Such protecting groups can employ any aryl , or halo . 50 useful agent to cleave the protecting group , thereby restoring

By “ nitro ” is meant an — NO , group . the reactivity of the unprotected reactive group . By “ nitroalkyl ” is meant an alkyl group , as defined herein , By “ salt ” is meant an ionic form of a compound or

substituted by one to three nitro groups . structure ( e . g . , any formulas , compounds , or compositions By “ nitroso ” is meant an — NO group . described herein ) , which includes a cation or anion com By “ oxo ” is meant an = group . 55 pound to form an electrically neutral compound or structure . By “ oxy ” is meant 0 Salts are well known in the art . For example , non - toxic salts By " perfluoroalkyl ” is meant an alkyl group , as defined are described in Berge S M et al . , “ Pharmaceutical salts , ” J .

herein , having each hydrogen atom substituted with a fluo Pharm . Sci . 1977 January ; 66 ( 1 ) : 1 - 19 ; and in “ Handbook of rine atom . Exemplary perfluoroalkyl groups include trifluo - Pharmaceutical Salts : Properties , Selection , and Use , " romethyl , pentafluoroethyl , etc . 60 Wiley - VCH , April 2011 ( 2nd rev . ed . , eds . P . H . Stahl and C .

By " perfluoroalkylene ” is meant an alkylene group , as G . Wermuth . The salts can be prepared in situ during the defined herein , having each hydrogen atom substituted with final isolation and purification of the compounds of the a fluorine atom . Exemplary perfluoroalkylene groups invention or separately by reacting the free base group with include difluoromethylene , tetrafluoroethylene , etc . a suitable organic acid ( thereby producing an anionic salt ) or By “ perfluoroalkyleneoxy ” is meant a perfluoroalkylene 65 by reacting the acid group with a suitable metal or organic

group , as defined herein , having an oxy group attached to salt ( thereby producing a cationic salt ) . Representative either end of the perfluoroalkylene group . Exemplary per - anionic salts include acetate , adipate , alginate , ascorbate ,

US 10 , 053 , 534 B2 15 16

an

aspartate , benzenesulfonate , benzoate , bicarbonate , bisul - include , independently , optionally substituted alkyl , alkenyl , fate , bitartrate , borate , bromide , butyrate , camphorate , cam alkynyl , alkaryl , alkheterocyclyl , alkcycloalkyl , alkanoyl , phorsulfonate , chloride , citrate , cyclopentanepropionate , alkoxy , alkoxyalkyl , alkoxycarbonyl , alkylsulfinyl , alkylsul digluconate , dihydrochloride , diphosphate , dodecylsulfate , fonyl , alkylsulfinylalkyl , alkylsulfonylalkyl , aminoalkyl , edetate , ethanesulfonate , fumarate , glucoheptonate , gluco - 5 aryl , arylalkoxy , aryloxy , aryloxycarbonyl , aryloyl , arylsul mate , glutamate , glycerophosphate , hemisulfate , heptonate , fonyl , arylsulfonylalkyl , azidoalkyl , carboxyaldehyde , car hexanoate , hydrobromide , hydrochloride , hydroiodide , boxyaldehydealkyl , carboxyl , cyano , cycloalkyl , hydroxyethanesulfonate , hydroxynaphthoate , iodide , lac - cycloalkoxy , haloalkyl , heteroaryl , heterocyclyl , heterocy tate , lactobionate , laurate , lauryl sulfate , malate , maleate , clyloxy , heterocyclyloyl , hydroxyalkyl , nitroalkyl , perfluo malonate , mandelate , mesylate , methanesulfonate , methyl - 10 roalkyl , perfluoroalkoxy , spirocyclyl , thioalkaryl , thio bromide , methylnitrate , methylsulfate , mucate , 2 - naphtha alkheterocyclyl , or thioalkoxy , as defined herein . The lenesulfonate , nicotinate , nitrate , oleate , oxalate , palmitate , sulfone can be unsubstituted or substituted . For example , the pamoate , pectinate , persulfate , 3 - phenylpropionate , phos sulfone can be substituted with one or more substitution phate , picrate , pivalate , polygalacturonate , propionate , groups , as described herein for alkyl and / or aryl . salicylate , stearate , subacetate , succinate , sulfate , tannate , 15 By “ sulfonyl ” is meant an - S ( O ) 2 - group . tartrate , theophyllinate , thiocyanate , triethiodide , toluene - By " sulfonamide " is meant an - S ( O ) 2 - NR3 — or an sulfonate , undecanoate , valerate salts , and the like . Repre - NR23 _ S ( O ) - group , in which R 3 is any useful moiety . sentative cationic salts include metal salts , such as alkali or Exemplary RP3 groups include H , optionally substituted alkaline earth salts , e . g . , barium , calcium ( e . g . , calcium alkyl , optionally substituted haloalkyl , optionally substituted edetate ) , lithium , magnesium , potassium , sodium , and the 20 alkoxy , optionally substituted alkaryl , optionally substituted like ; other metal salts , such as aluminum , bismuth , iron , and aryl , or halo . zinc ; as well as nontoxic ammonium , quaternary ammo By “ thioalkaryl ” is meant a thioalkoxy group , as defined nium , and amine cations , including , but not limited to herein , substituted with an aryl group , as defined herein . ammonium , tetramethylammonium , tetraethylammonium , By “ thioalkheterocyclyl ” is meant a thioalkoxy group , as methylamine , dimethylamine , trimethylamine , triethylam - 25 defined herein , substituted with a heterocyclyl group , as ine , ethylamine , pyridinium , and the like . Other cationic defined herein . salts include organic salts , such as chloroprocaine , choline , By “ thioalkoxy ” is meant an alkyl group , as defined dibenzylethylenediamine , diethanolamine , ethylenediamine , herein , attached to the parent molecular group through a methylglucamine , and procaine . Yet other salts include sulfur atom . Exemplary unsubstituted thioalkoxy groups ammonium , sulfonium , sulfoxonium , phosphonium , imi - 30 include C - thioalkoxy . nium , imidazolium , benzimidazolium , amidinium , guani - By “ thioamido " is meant C ( S ) NRMRN2 , where each of dinium , phosphazinium , phosphazenium , pyridinium , etc . , RM and RN2 is , independently , H or optionally substituted as well as other cationic groups described herein ( e . g . , alkyl , or RM and RN2 , taken together with the nitrogen atom optionally substituted isoxazolium , optionally substituted to which each are attached , form a heterocyclyl group , as oxazolium , optionally substituted thiazolium , optionally 35 defined herein . substituted pyrrolium , optionally substituted furanium , By “ thio " is meant an - S group By “ thiol ” is meant an optionally substituted thiophenium , optionally substituted SH group . imidazolium , optionally substituted pyrazolium , optionally By " triflate ” is meant an OSO , CF , or - OTf group . substituted isothiazolium , optionally substituted triazolium , By “ triflimide ” is meant an - N ( SO2 - CF3 ) 2 or - NTf , optionally substituted tetrazolium , optionally substituted 40 group . furazanium , optionally substituted pyridinium , optionally By “ trifyl ” or “ Tf ' is meant an SO2 – CF3 group . substituted pyrimidinium , optionally substituted By " attaching , " " attachment , ” or related word forms is pyrazinium , optionally substituted triazinium , optionally meant any covalent or non - covalent bonding interaction substituted tetrazinium , optionally substituted pyridazinium , between two components . Non - covalent bonding interac optionally substituted oxazinium , optionally substituted pyr - 45 tions include , without limitation , hydrogen bonding , ionic rolidinium , optionally substituted pyrazolidinium , option interactions , halogen bonding , electrostatic interactions , it ally substituted imidazolinium , optionally substituted isox - bond interactions , hydrophobic interactions , inclusion com azolidinium , optionally substituted oxazolidinium , plexes , clathration , van der Waals interactions , and combi optionally substituted piperazinium , optionally substituted nations thereof . piperidinium , optionally substituted morpholinium , option - 50 As used herein , the terms " top , ” “ bottom , " " upper , " ally substituted azepanium , optionally substituted aze - “ lower , " " above , ” and “ below ” are used to provide a relative pinium , optionally substituted indolium , optionally substi - relationship between structures . The use of these terms does tuted isoindolium , optionally substituted indolizinium , not indicate or require that a particular structure must be optionally substituted indazolium , optionally substituted located at a particular location in the apparatus . benzimidazolium , optionally substituted isoquinolinum , 55 Other features and advantages of the invention will be optionally substituted quinolizinium , optionally substituted apparent from the following description and the claims . dehydroquinolizinium , optionally substituted quinolinium , optionally substituted isoindolinium , optionally substituted BRIEF DESCRIPTION OF THE DRAWINGS benzimidazolinium , and optionally substituted purinium ) .

By “ spirocyclyl ” is meant an alkylene diradical , both ends 60 FIG . 1 shows an exemplary reaction scheme for reacting of which are bonded to the same carbon atom of the parent an initial polymer structure having formula ( I ) in the pres group to form a spirocyclyl group and also a heteroalkylene ence of one or more reactive handles ( RA ) , thereby provid diradical , both ends of which are bonded to the same atom . ing a polymer structure having formula ( II ) . By " sulfinyl ” is meant an - S ( O ) - group . FIGS . 2A - 2B shows schematics of exemplary polymer By “ sulfo " is meant an - S ( O ) 2OH group . 65 structures having one or more reactive handles ( RA ) . Pro By " sulfone ” is meant R ' - S ( O ) 2 - R " , where R ' and R " vided are exemplary polymer structures ( A ) having formulas

is an organic moiety . Exemplary groups for R ' and R " ( IIa ) to ( IId ) and ( B ) having formulas ( Ile ) to ( IIj ) .

17 US 10 , 053 , 534 B2

18 FIGS . 3A - 3C shows schematics of exemplary reagents Crafts aryl acylation reaction ; and ( C ) an exemplary reaction

having one or more reactive end groups ( R ) . Provided are scheme showing the reaction between a silver triflate reagent exemplary reagent structures ( A ) having formulas ( III ) and ( AgoTf ) and a benzoyl chloride , a potential source for a ( IIIa ) , ( B ) having formulas ( IIIb ) and ( IIIc ) , and ( C ) having reactive handle , and then further functionalization with a formula ( IIId ) . 5 phenyl group of a polymer . FIGS . 4A - 4C shows schematics of exemplary reaction FIGS . 11A - 11C shows reaction of a labeled DAPP in the

schemes to provide polymer structures with one or more presence of a reagent to provide a reactive handle . Provided reactive handles ( RM ) . Provided are ( A ) an exemplary reac are ( A ) an exemplary reaction scheme for reacting a F - la tion of a labeled Diels - Alder poly ( phenylene ) polymer ( la beled DAPP in the presence of a reagent ( e . g . , RA — X , such beled “ F - labeled DAPP ” ) in the presence of a reagent ( e . g . , 10 as F - Ar — C ( O ) - Cl ) to form a DAPP ( II - 13 ) having two RH — X , such as R41 — Ar - C ( O ) - X ) to form a DAPP ( II - 1 ) having six reactive handles RH appended to all six reactive handles RH appended to two pendent aryl groups of

the DAPP ( e . g . , in which RH is F — Ar — C ( 0 ) ) ; ( B ) an pendent aryl groups of the DAPP ( e . g . , in which RA is RH1 - Ar - C ( O ) ) ; ( B ) an exemplary reaction of a Diels NMR spectrograph of the F - labeled DAPP ; and ( C ) an Alder poly ( phenylene ) polymer ( labeled “ DAPP ” ) in the 15 exemplary reaction scheme for reacting a R “ - containing presence of a reagent ( e . g . , RH — X , such as RHI — Ar - C DAPP in the presence of a reagent ( e . g . , R4 - X , such as ( 0 ) - X ) to form a DAPP ( II - 2 ) having three reactive CH30 — Ar — 0 - H ) to form a DAPP ( II - 14 ) having a handles RH appended to half of the pendent aryl groups of functional group R4 attached to each of the two reactive the DAPP ( e . g . , in which RH is RHI — Ar — C ( 0 ) ) ; and ( C ) handles RH ( e . g . , in which the reacted RH is — Ar - C ( O ) - , an exemplary reaction of a DAPP ( II - 3 ) having four reactive 20 and in which R4 is CH20 - Ar - 04 ) . handles appended to four of the pendent aryl groups of the FIG . 12 shows an exemplary reaction scheme for reacting DAPP ( e . g . , in which RH is RA — Ar - C ( O ) - ) in the a F - labeled DAPP in the presence of a reagent ( e . g . , RA — X , presence of an acid ( e . g . , H2SO4 ) to form a DAPP ( II - 4 ) such as F - Ar — S02C1 ) and a metal salt ( e . g . , M ( OTf ) ) to having both reactive handles and acid groups appended to form a DAPP ( II - 15 ) having nine reactive handles RH the pendent aryl groups . 25 appended to six pendent aryl groups and three backbone aryl

FIGS . 5A - 5B shows schematics of further exemplary groups of the DAPP ( e . g . , in which RH is F — Ar - S0 , - ) . reaction schemes to provide polymer structures with one or FIG . 13 shows an exemplary reaction scheme for per more reactive handles ( R " ) . Provided are ( A ) an exemplary forming a Diels - Alder reaction to generate the Diels - Alder reaction of a Diels - Alder poly ( phenylene ) polymer ( labeled poly ( phenylene ) ( DAPP , 3 * ) and for performing a Friedel “ DAPP ” ) in the presence of a reagent ( e . g . , RH — X , such as 30 cm Crafts aryl acylation reaction to generate the DAPP ( II - 16 ) ( RHI ) 6 - Ar - C ( O ) - X ) to form a DAPP ( II - 5 ) having three having two reactive handles . reactive handles RH appended to half of the pendent aryl FIG . 14 shows further exemplary compounds having groups of the DAPP ( e . g . , in which RH is ( RH ) 6 - Ar C ( 0 ) ) ; and ( B ) an exemplary reaction of a Diels - Alder reactive handles . Provided is compound ( II - 17 ) having reac poly ( phenylene ) polymer ( labeled “ DAPP ” ) in the presence 35 live 5 tive handles ( e . g . , an R " , such as an optionally substituted of a reagent ( e . g . , RH — X , such as ( RH ) 6 - Ar - S02 - X ) to aryloyl ) in combination with acidic moieties ( e . g . , an RS form a DAPP ( IL - 6 ) having three reactive handles RH group , such as — SO3H ) . Also provided is compound ( 11 - 18 ) appended to half of the pendent aryl groups of the DAPP having various types of reactive handles ( e . g . , an R “ , such ( e . g . , in which RH is ( RA ) 6 - Ar — S02 - ) . as an optionally substituted alkaryl group that is substituted FIGS . 6A - 6C shows schematics of exemplary copolymer 40 with an aminoalkyl group and / or an optionally substituted

structures having a first segment , a linking segment , and a alkaryl group that is substituted with a perfluoroalkyl second segment . Provided are exemplary polymer structures group ) . For compound ( II - 18 ) , each Ak is independently , an ( A ) having formula ( IV ) , ( B ) having formula ( V ) , and ( C ) optionally substituted alkylene group ( e . g . , any herein , such having formula ( Va ) . as an optionally substituted methylene , ethylene , etc . ) . In

FIG . 7 shows an exemplary reaction scheme for reacting 45 each of these compounds , m can be any useful number ( e . g . , the reactive handles ( RH ) of an initial polymer structure any herein , such as of from about 40 to about 100 ) . having formula ( II ) in the presence of one or more functional groups ( R4 ) , thereby providing a further functionalized DETAILED DESCRIPTION OF THE polymer structure having formula ( VI ) . INVENTION

FIGS . 8A - 8C shows schematics of exemplary polymer 50 structures having one or more reactive handles ( RH ) . Pro - The present invention relates to polymer structures having vided are ( A ) an exemplary schematic of various portions of various reactive handles RH . In particular embodiments , the DAPP that can be appended with a reactive handle R these reactive handles allow the underlying polymer ( e . g . , ( e . g . , on one or more pendent groups of DAPP ) or with an pendent groups and / or backbone groups of the polymer ) to acidic group ( e . g . , on the backbone and / or one or more 55 be further functionalized with one or more functional groups pendent groups of DAPP ) . Also provided are exemplary ( e . g . , acidic moieties ) . Described herein are structures for polymer structures ( B ) having formulas ( Ilk ) to ( IIp ) and ( C ) such polymers having reactive handles , as well as methods having formulas ( Ilq ) and ( IIr ) . for making and functionalizing such polymers .

FIG . 9 shows schematics of exemplary polymer structures Polymers having formulas ( 11 - 7 ) to ( II - 12 ) , which include one exem - 60 The present invention encompasses polymers , including plary reactive handle RH on a pendent aryl group Arl . copolymers . Exemplary polymer include any described

FIGS . 10A - 10C shows exemplary reaction schemes herein , such as non - limiting generic structure provided in involving Diels - Alder polyphenylene polymers ( DAPPs ) . formulas ( II ) , ( la ) , ( IIb ) , ( IIC ) , ( IId ) , ( le ) , ( IIf ) , ( Ilg ) , ( IIh ) , Provided are ( A ) an exemplary reaction scheme for reacting ( Ili ) , ( IIj ) , ( IIk ) , ( III ) , ( Ilm ) , ( IIn ) , ( Ilo ) , ( IIp ) , ( IIq ) , ( IIr ) , DAPP to conduct a Friedel Crafts alkyl acylation reaction , 65 ( III ) , ( IIIa ) , ( IIIb ) , ( IIIc ) , ( IIId ) , ( IV ) , ( V ) , ( Va ) , and ( VI ) , as thereby producing an alkyl acylated DAPP ; ( B ) exemplary well as particular structures provided as structures ( 11 - 1 ) , reaction schemes for reacting DAPP to conduct a Friedel ( II - 2 ) , ( II - 3 ) , ( II - 4 ) , ( II - 5 ) , ( II - 6 ) , ( II - 7 ) , ( II - 8 ) , ( II - 9 ) , ( II - 10 ) ,

US 10 , 053 , 534 B2 19 20

( II - 11 ) , ( II - 12 ) , ( II - 13 ) , ( II - 14 ) , ( II - 15 ) , ( II - 16 ) , ( II - 17 ) , and fluorine , such as 9F ; nitrogen , e . g . , 15N ; or oxygen , ( II - 18 ) ( see FIGS . 4A - 4C , 5A - 5B , 9 , 11A , 11C , and 12 - 14 ) , e . g . , " ' 0 ) , a spin label , an isotopic label , a mass label , a including salts thereof . fluorescent label , a dye , etc . Of these . formulas ( III ) , ( Illa ) , ( IIIb ) . ( IIIc ) , ( Illd ) , ( V ) . In yet other embodiments , each of Art and Ar ” is , inde

and ( Va ) are considered to be reagents having one or more 5 pe e 5 pendently , configured to reduce meta linkages . Thus , in some instances , each of Art and Ar is , independently , a reactive end groups . Formula ( IV ) is considered to be a bivalent linker formed by removing a hydrogen atom from copolymer . In particular embodiments , the copolymer of the opposite faces of an aryl group . Examples of such linkers

invention includes a first segment , a second segment , and at include 1 , 4 - benzenediyl ( or 1 , 4 - phenylene ) , 2 , 7 - phenan least one linking segment connecting at least one first thrylene ( or 2 , 7 - phenanthrenediyl ) , 1 , 5 - naphthylene ( or 1 , 5 segment with at least one second segment . The second napthalenediyl ) , etc . For example , the polymer can include segment can be a hydrophilic segment or a hydrophobic a structure of Formula ( IId ) having Art as a R - substituted segment . The first segment can include at least one reactive 1 , 4 - phenylene and Ar as an R² - substituted , RA - substituted handle RH . 1 , 4 - phenylene .

In one embodiment , a polymer includes the structure of 15 A polymer can include any useful number of structures of 15 formula ( II ) . In some embodiments , the polymer includes m formula ( II ) , including salts thereof . As can be seen in FIG . structures , where m is an integer of from about 1 to 1000 1 , formula ( II ) is a generic structure encompassing other ( e . g . , from about 1 to 500 ) . structures ( e . g . , formula ( IIa ) ) . The polymer can include any Reactive handles RH can be present on the same polymer

useful number of reactive handles R “ disposed on pendent or on the same segment of the polymer with any other aryl groups and / or backbone aryl groups . The polymer can 20 different type of substitutions , e . g . , acidic substitutions ( e . g . , include any useful type of reactive handles ( e . g . , reactive RS , RP , and / or R " , as well as combinations thereof ) and R handles R4 ) , as well as any useful number of such handles substitutions . In particular , the use of acidic moieties and ( e . g . , h handles , where h can be 0 , 1 , 2 , 3 , 4 , or 5 , and / or electron - withdrawing moieties could provide orthogonal where at least one h is not 0 ) . chemistries to control and optimize performance ( e . g . , by

The polymer can include any useful type of pendent 25 employing acidic moieties to control ion conduction ) and substituents ( e . g . , pendent substituents RH and / or R ) , as durability ( e . g . , by employing electron - withdrawing moi well as any useful number of such substituents on each aryl eties to reduce oxidation ) . Further , the presence of a reactive group ( e . g . , h substituents for RH and / or q substituents for handle Rº allows the polymer to be further functionalized R ? , where each of h and q is , independently , 0 , 1 , 2 , 3 , 4 , or ( e . g . , with one or more functional groups R4 , which can be 5 , and / or where at least one h is not 0 ) . For any structure 30 any groups described herein , including those described for described herein , each R3 is , independently , a reactive RS , RP , RC , and / or RF ) . In one instance , each pendent aryl handle RH , an acidic moiety ( e . g . , RS , R , RC , or any group is substituted with an R4 , an R™ , an R ? , an RC , and / or described herein ) , an electron - withdrawing moiety ( e . g . , RF an RF . Optionally , one or more backbone aryl groups can be or any described herein ) , or an inert substituent ( e . g . , H , further substituted with an R™ , an RS , an RP , an RC , and / or halo , optionally substituted alkyl , optionally substituted 35 an R . alkoxy , etc . ) . In some embodiments , each and every R * is , As seen in FIG . 2A , formulas ( IIa ) to ( IId ) provide independently , RM , RS , RP , R " , or R . In some embodi - polymers having various combinations of structures for the ments , fully substituted pendent groups ( e . g . , R is not H ) bridging group Art and the connecting group Ar . For can provide polymers with enhanced proton conduction and example , formula ( Ila ) includes a connecting group ArM ; durability characteristics . 40 formula ( IIb ) includes a connecting group that is a R2 - sub

The polymer can also include any useful backbone struc - stituted 1 , 4 - phenylene group ; formula ( IIC ) includes a con ture . For instance , in formula ( II ) , the backbone includes necting group that is a R2 - substituted , RA - substituted 1 , 4 three groups , i . e . , two RP - substituted aryl groups and a phenylene group ; and formula ( Ild ) includes a bridging bridging group Are optionally including a reactive handle group that is a RP - substituted 1 , 4 - phenylene group and a RH . The polymer can include any useful type of backbone 45 connecting group that is a R2 - substituted , RH - substituted substituents ( e . g . , backbone substituents R or RH disposed 1 , 4 - phenylene group . on a backbone aryl group ) , as well as any useful number of As seen in FIG . 2B , formulas ( Ile ) to ( IIj ) provide such substituents on each group ( e . g . , h substituents for RA polymers having various R3 and RA substituents on pendent and / or q substituents for R ' , where each of h and q is , aryl groups , as well as various Rl and RA substituents on independently , 0 , 1 , 2 , 3 , 4 , or 5 , and / or where at least one 50 backbone aryl groups . For instance , formula ( Ile ) provides a h is not 0 ) . For any structure described herein , each R ' is , polymer having both Rand R substituents on some of the independently , a reactive handle ( RA ) , an acidic moiety ( e . g . , pendent aryl groups , whereas formula ( IIf ) provides a poly RS , RP , RC , or any described herein ) , an electron - withdraw mer having either R3 or R™ substituents on the pendent aryl ing moiety ( e . g . , R or any described herein ) , or an inert groups . In other instances , formulas ( IIg ) to ( Ilj ) provide substituent ( e . g . , H , halo , optionally substituted alkyl , 55 polymers having various levels of RH substitution . As can be optionally substituted alkoxy , etc . ) . In some embodiments , seen , formulas ( Ilg ) and ( IIh ) include RH substituents on each and every Rl is , independently , RH , RS , RP , RC , or RF . three of the pendent aryl groups . In another instance , for

Each of bridging group Art and connecting group Am can mula ( Ili ) includes RA substituents on all pendent and be any useful bivalent linker . In particular embodiments , backbone aryl groups , whereas formula ( Ilj ) includes RH each of Art and ArM is , independently , includes an optionally 60 substituents on all pendent aryl groups . substituted arylene group . In some embodiments , each of Polymer Reagents Art and Am is , independently , an optionally substituted The present invention also includes reagents having any arylene group . In other embodiments , each of Art and Am useful polymer segment described herein . For instance , the is , independently , substituted with 1 , 2 , 3 , or 4 RH reagent can include a polymer segment disposed between substituent ( s ) , RS substituent ( s ) , R? substituent ( s ) , RC sub - 65 two reactive end groups , where each end group can be the stituent ( s ) , RF substituent ( s ) , or label ( s ) . Exemplary labels same or different . The polymer segment can be any include a detectable label , such as an NMR label ( e . g . , described herein ( e . g . , a structure provided in formula ( II ) ,

22 US 10 , 053 , 534 B2

21 ( IIa ) , ( IIb ) , ( IIC ) , ( IId ) , ( le ) , ( IIf ) , ( IIg ) , ( IIh ) , ( Ili ) , ( IIj ) , ( Ilk ) , includes a sublink having a structure similar to that of ( Ill ) , ( IIm ) , ( IIn ) , ( IIo ) , ( Ilp ) , ( Ilq ) , and ( IIr ) , as well as Formula ( II ) but lacking aryl group Am . particular structures provided as structures ( II - 1 ) , ( II - 2 ) , Copolymers ( II - 3 ) , ( II - 4 ) , ( II - 5 ) , ( II - 6 ) , ( II - 7 ) , ( II - 8 ) , ( II - 9 ) , ( II - 10 ) , ( II The present invention also includes copolymers . In one 11 ) , ( II - 12 ) , ( II - 13 ) , ( II - 14 ) , ( II - 15 ) , ( II - 16 ) , ( II - 17 ) , and 5 embodiment , the copolymer includes the structure of for ( II - 18 ) ) . In addition , the polymer segment can include a mula ( IV ) , including salts thereof . As can be seen in FIG . second segment ( eg . Ap * ) , such as any described herein . 6A , formula ( IV ) is a generic structure . Similar to formula

Optionally , a sublink L ' can be present between the ( II ) described above , the copolymer structure includes RH substituted pendent and / or backbone aryl groups , R ' - sub polymer segment and a reactive end group . The sublink L ' 10 stituted aryl groups , bridging group Ar , connecting group can be composed of any useful linkage , such as any Am , pendent substituents R " , and m described herein ( e . g . , those described for linking segment units . Thus , the description for these substituents provided for formula ( II ) L ) . applies equally to formula ( IV ) . In some embodiments , each The reactive end group can be any useful group config of Art and ArM is , independently , an optionally substituted

ured to react with a second reactive end group . In this way , 15 phenylene . In other embodiments , each of Art and Am is . ordered copolymer block structures can be synthesized by independently , an optionally substituted 1 . 4 - phenylene , e . g . . selectively placing reactive end groups on the ends of blocks Art as a R - substituted 1 , 4 - phenylene and / or Ar as an or segments to form polymer reagents , and then reacting that R2 - substituted 1 , 4 - phenylene . polymer reagent to place the segments in an end - to - end FIG . 6B provides formula ( V ) , which is another generic fashion in the copolymer . A skilled artisan would understand 20 structure including a first segment , a linking segment , a how to place reactive end groups in a polymer reagent in second segment , and two reactive end groups R ' . The first order to form a copolymer with the desired configuration or segment can be any described herein ( e . g . , a structure having order . formula ( II ) ) . The reactive end group R can be any

The reactive end group R is usually placed on the ends described herein . As seen in FIG . 6C , the structure of of a first polymer reagent , as well as on the ends of the 25 formula ( Va ) includes a reactive end group R + that is an second polymer reagent . Then , a first reactive end group on optionally substituted aryl group ( e . g . , an aryl group having the first polymer reagent reacts with the second reactive end h number of RH groups ) . group on a second polymer reagent . The first and second Formulas ( IV ) and ( V ) also include additional groups , reactive end groups can be chosen from a pair of co - reactive including a linking segment L and a second segment Ar * of groups . For example , such pairs of co - reactive groups 30 n units . The linking segment L can be any useful linkage include ( i ) a nucleophile for use with ( ii ) an electrophile ; ( i ) ( e . g . , any herein ) , including those to form a covalent bond an optionally substituted aryl group ( e . g . , having a - C ( OR between the two segments . In some embodiments , the group , where R ' is an aryl group having one or more halo ) linking segment includes those composed of structures , or a for use with ( ii ) an optionally substituted aryl group ( e . g . , portion of such structures , in the first segment and / or the having a _ ORPr group , where RP " is H or an O - protecting 35 second segment . Exemplary linking segments L include a group that can be deprotected prior to conducting a reac - covalent bond , an optionally substituted alkylene , an option tion ) ; ( i ) an optionally substituted aryl group ( e . g . , having a ally substituted heteroalkylene , an optionally substituted - C ( O ) R ' group , where R is an aryl group having one or a lkyleneoxy , an optionally substituted heteroalkyleneoxy , an more halo ) for use with ( ii ) an optionally substituted alkoxy optionally substituted arylene , an optionally substituted group ( e . g . , such as ORF , where RF is H or an O - pro - 40 aryleneoxy , an Ar * unit , or a structure of formula ( II ) . tecting group that can be deprotected prior to conducting a The copolymer having formulas ( IV ) and ( V ) can have reaction ) ; ( i ) an optionally substituted aryl group for use any useful second segment Ar * . In some embodiments , Ar * with ( ii ) an optionally substituted alkoxy group ( e . g . , such as includes a structure of formula ( II ) ( e . g . , where each Rºis H , - OR ? " , where RP is H or an O - protecting group that can optionally substituted alkyl , or R? ; or where the number of be deprotected prior to conducting a reaction ) ; ( i ) an option - 45 RS substituents in Ar * is less than the number of RS and / or ally substituted alkynyl group for use with ( ii ) an optionally R ? substituents in the hydrophilic segment ) ; a hydrophobic substituted azido group , which can participate in a Huisgen subunit ; a sulfone subunit ( e . g . , a subunit including an 1 , 3 - dipolar cycloaddition reaction , as well as ( i ) an option - SO2 - group ) ; an arylene sulfone subunit ( e . g . , ally substituted diene having a 4 , electron system for use ( Ar ) , — SO , — ( Ar ) , where Ar is an optionally substi with ( ii ) an optionally substituted dienophile or an optionally 50 tuted arylene group , as defined herein , and each a and b is substituted heterodienophile having a 2n electron system , an integer of about 0 to 10 and at least one of a or b is 1 or which can participate in a Diels - Alder reaction . For the more ) ; an ether sulfone subunit ( e . g . , — ( X ) . - S0 , co - reactive groups above , reagent ( i ) reacts with reagent ( ii ) ( XP ) 1 - 0 or — X1 - 0 X2 _ S0 , – , where each X and in each pair . In one instance , the reactive group is RA ( e . g . , X² is , independently , any useful group , such as optionally any described herein ) . 55 substituted arylene or optionally substituted alkylene , and An exemplary polymer reagent is provided as structure each a and b is an integer of about 0 to 10 and at least one

( III ) in FIG . 3A . As can be seen , polymer reagent ( III ) of a or b is 1 or more ) ; an arylene ether subunit ( e . g . , includes a two reactive end groups R with a polymer ( Ar ) , - 0 ( Ar ) , where Ar is an optionally substituted segment ( in brackets ) placed between the reactive end arylene group , as defined herein , and each a and b is an groups . For this exemplary reagent , the optional sublink L ' 60 integer of about 0 to 10 and at least one of a or b is 1 or is located between the polymer segment and one of the more ) ; an arylene ketone subunit ( e . g . , ( Ar ) , - C ( O ) reactive end groups . For reagent ( III ) , the polymer segment ( Ar ) — , where Ar is an optionally substituted arylene group , is that of formula ( II ) , but any formula or structure herein as defined herein , and each a and b is an integer of about 0 can be employed for this polymer segment . to 10 and at least one of a or b is 1 or more ) ; a perfluoroalkyl

Further exemplary polymer reagents are provided as 65 subunit ( e . g . , ( CF2 ) A4 , where f1 is an integer of 1 to structure ( IIIa ) to ( IIId ) in FIG . 3A - 3C . Exemplary reagents about 16 ) ; or a perfluoroalkoxy subunit ( e . g . , O ( CF2 ) A - , include a polymer having structure ( IIIa ) to ( IIId ) , which ( CF2 ) O - , - O ( CF2 ) , CF ( CF3 ) O ( CF23124 , CFO

US 10 , 053 , 534 B2 23 24

su

( CF2ACF ( CF3 ) O ( CF2 ) 2 - , where each fl and f2 is , inde - described herein , including those described for R9 , RP , RC , pendently , an integer of 1 to about 16 ) . and / or R ? ) . In one instance , each pendent aryl group is

In some embodiments , formulas ( IV ) and ( V ) include a substituted with an RH , an RS , an RP , an Rº , and / or an RF . second segment Ar * that is a hydrophobic segment . In some Optionally , one or more backbone aryl groups can be further embodiments , the second segment Ar * is a hydrophobic 5 substituted with an RH , an RS , an RP , an RC , and / or an RF . segment having one or more electron - withdrawing moieties Functional Moieties ( e . g . , RF ) . In particular embodiments , each pendent aryl The present invention includes the use of functional group in the polymer or a segment thereof is substituted with moieties , such as reactive handles ( e . g . , R " ) , acidic moieties an RF substitution , where each substitution may be the same ( e . g . , RS , RP , or R ) , electron - withdrawing moieties ( e . g . , or different . In other embodiments , both pendent and back - 10 R ) , and functional groups . Any number of these functional bone aryl groups are each , independently , substituted with moieties can be present on the polymer ( e . g . , the polymer an RF substitution . backbone aryl groups and / or pendent aryl groups ) .

In other embodiments , formulas ( IV ) and ( V ) include a Exemplary reactive handles ( e . g . , RH ) include any useful second segment Ar * that is a hydrophobic segment . In some group , such as H , optionally substituted alkyl , optionally embodiments , the second segment Ar * is a hydrophilic 15 substituted haloalkyl , optionally substituted perfluoroalkyl , segment that includes the two RP - substituted aryl groups and optionally substituted heteroalkyl , halo , optionally substi a bridging group Art . Thus , in some embodiments , at least tuted aryl , optionally substituted alkaryl , optionally substi one substituent in this hydrophilic segment ( e . g . , substitu tuted arylalkoxy , optionally substituted aryloxy , optionally ents R1 , R2 , or R3 ) is a hydrophilic moiety ( e . g . , an acidic substituted aryloxycarbonyl , optionally substituted aryloyl , moiety , such as any R " , RP , and / or Rº described herein or 20 optionally substituted arylcarbonylalkyl , optionally substi any moiety including a sulfonyl group or a phosphoryl tuted arylsulfonyl , and optionally substituted arylsulfonyl group ) . In some embodiments , the hydrophilic segment alkyl . In one instance , at least one RH includes an optionally includes one or more acidic moieties ( e . g . , R " , RP , and / or substituted aryl group ( e . g . , an optionally substituted aryl RC , as well as combinations thereof ) on only the pendent group including a halo , a haloalkyl , a perfluoroalkyl , a aryl groups . Exemplary hydrophilic segments include those 25 hydroxyl , or an alkoxy group ) . having RS - substituted pendent aryl groups , RP - substituted In some embodiments , the reactive handle RH includes pendent aryl groups , and R - substituted backbone aryl “ L ” Art or LH - AKH , in which Ar ” is an optionally groups . substituted aryl and in which Akh is an optionally substi

A copolymer can include any useful number or ratio of tuted alkyl or optionally substituted heteroalkyl . In particu first and second segments ( e . g . , hydrophilic and hydropho - 30 lar embodiments LA is any useful covalent bond or any bic segments ) . In some embodiments , formulas ( IV ) and ( V ) useful linker ( e . g . , any described herein ) . In some embodi include m number of first segments ( e . g . , hydrophilic seg m ents , Art or AKA is substituted with one or more substitu ments ) and n number of second segments ( e . g . , hydrophobic e nts selected from the group of halo , cyano , optionally segments ) , where each of m and n is , independently , an substituted haloalkyl , optionally substituted perfluoroalkyl , integer of from about 1 to 1000 . In other embodiments , the 35 optionally substituted nitroalkyl , and optionally substituted m ( the number of first segments ) is minimized in order to alkyl . minimize swelling of the copolymer . For example , in some FIG . 8B provides exemplary polymers having a structure instances , m < n . In other instance , n is at least about 5 times that includes RA substituents selected from - LA / Art and greater than m ( e . g . , n is about 10 times greater than m , or — LA — AKA . As can be seen , the polymer can include one or n is about 20 times greater than m ) . In yet other instances , 40 more RH that is — L — Ar . In some embodiments , the Ar m is of from about 1 to 100 , and n is of from about 5 to 500 aryl - containing R substituent is installed on each aryl group ( e . g . , m is of from about 1 to 50 , and n is of from about 5 of the polymer ( e . g . , as in a structure having formula ( IIR ) ) . to 500 ; m is of from about 1 to 50 , and n is of from about In other embodiments , the Art aryl - containing RH substitu 10 to 100 ; m is of from about 1 to 10 , and n is of from about e nt is installed on each pendent aryl group of the polymer 5 to 500 ; m is of from about 1 to 20 , and n is of from about 45 ( e . g . , as in a structure having formula ( Ilm ) ) . In yet other 20 to 400 ; and m is of from about 1 to 10 , and n is of from embodiments , the Art aryl - containing RH substituent is about 100 to 200 ) . In some instances , m can be about 5 . 6 and installed on three pendent aryl groups of the polymer ( e . g . , n can be about 60 . 7 or 121 . 4 . In other instances , m is of from as in a structure having formula ( 110 ) ) . about 1 to 20 , and n is of from about 20 to 400 . In some embodiments , the Art aryl - containing R # sub

For any polymer herein , including any copolymer herein , 50 stituent is [ 4 – Ar ” , in which Art is an RHl - substituted each and every R can be independently , RA , RS , R , RC , phenyl group . Furthermore , any number h of such RH and / or R? . For instance , in some embodiments , each aryl substituents can be installed on each aryl group . RH can be group in the polymer or a segment thereof is substituted with any useful substituent , such as amino , amido , azido , nitro , an RH , an RS , an RP , and / or an RC substitution , where each nitroso , halo , as well as any described for an aryl group ( e . g . , substitution may be the same or different . Reactive handles 55 substituents ( 1 ) - ( 47 ) as defined herein for aryl ) . As seen in RH can be present on the same polymer or on the same FIG . 8C , in other embodiments , the Art aryl - containing RH segment of the polymer with any other different type of substituent is installed on three pendent aryl groups of the substitutions , e . g . , acidic substitutions ( e . g . , RS , RP , and / or polymer ( e . g . , as in a structure having formula ( IIq ) ) . RC , as well as combinations thereof ) and RF substitutions . In In other embodiments , the Art aryl - containing R # sub particular , the use of acidic moieties and electron - withdraw - 60 stituent is - L - Art , in which LH is a sulfonyl group and ing moieties could provide orthogonal chemistries to control in which Art is a halo - substituted phenyl group ( e . g . , and optimize performance ( e . g . , by employing acidic moi - pentafluorophenyl , tetrafluorophenyl , trifluorophenyl , dif eties to control ion conduction ) and durability ( e . g . , by luorophenyl , or monofluorophenyl ) . As seen in FIG . 9 , employing electron - withdrawing moieties to reduce oxida exemplary polymers include structures having formula ( II tion ) . Further , the presence of a reactive handle RH allows 65 7 ) or structures having formula ( II - 8 ) . the polymer to be further functionalized ( e . g . , with one or In yet other embodiments , the Art aryl - containing RH more functional groups R4 , which can be any groups substituent is - L " Ar ” , in which is a carbonyl group and

US 10 , 053 , 534 B2 25 26

in which Art is a halo - substituted phenyl group ( e . g . , substituents selected from the group of halo , haloalkyl , nitro , pentafluorophenyl , tetrafluorophenyl , trifluorophenyl , dif - nitroso , alkoxy , etc . ) . In another instance , RH includes luorophenyl , or monofluorophenyl ) . As seen in FIG . 9 , C ( O ) - Ph , in which Ph is substituted with h1 number of exemplary polymers include structures having formula ( II - RH , where RH is selected from the group of halo , 9 ) or structures having formula ( II - 10 ) . 5 haloalkyl , nitro , nitroso , alkoxy , etc . , and where h1 is an As can also be seen in FIG . 8B , the polymer can include integer of from 1 to 5 ) .

one or more RH that is LH AKH . In some embodiments , FIG . 4A shows an exemplary reactive handle RH , in the Aka alkyl - containing RH substituent is installed on each which RH is located in the para position in relation to the aryl group of the polymer ( e . g . , as in a structure having C ( O ) - linker of RH . As can be seen , any number of aryl formula ( III ) ) . In other embodiments , the Akt alkyl - con - 10 groups in the underlying DAPP can be substituted . For taining RF substituent is installed on each pendent aryl instance , in the polymer of structure ( II - 1 ) , each pendent aryl group of the polymer ( e . g . , as in a structure having formula group ( i . e . , aryl groups Arl to Ar6 ) includes a RH substituent ( IIn ) ) . In yet other embodiments , the Ak " alkyl - containing of C ( O ) - ( p - RA ) - Ph . In another instance , only the back R™ substituent is installed on three pendent aryl groups of bone aryl groups ( i . e . , aryl groups Ar7 to Ar9 ) are substituted the polymer ( e . g . , as in a structure having formula ( IIp ) ) . 15 ( e . g . , with one or more R " , such as any herein ) . In yet

In some embodiments , the Aka alkyl - containing RH sub - another instance , the connecting group Am ( labeled aryl stituent is LA - AKH , in which AKH is an RH - substituted group Ar10 ) is substituted ( e . g . , with one or more RH , such C / - alkyl group . Furthermore , any number h of such R as any herein ) . Optionally , the connecting group Am can substituents can be installed on each aryl group , and any include a label ( e . g . , halo ) . number h1 of CRHRHI — groups can be present within 20 Any useful number of aryl groups in the polymer can the RA substituent , in which each Rl can be the same or include RH . For instance , as seen in FIG . 4B , the polymer of different . RH can be any useful substituent , such as amino , structure ( II - 2 ) includes three pendent aryl groups , in which amido , azido , nitro , nitroso , halo , as well as any described each of these pendent groups includes a R™ substituent of for an aryl group ( e . g . , substituents ( 1 ) - ( 27 ) as defined herein - C ( O ) - ( P - RAT ) - Ph . In some instances , each pendent aryl for alkyl ) . As seen in FIG . 8C , in other embodiments , the 25 group is substituted . In other instances , only some of the AKH alkyl - containing RP substituent is installed on three pendent groups are substituted . pendent aryl groups of the polymer ( e . g . , as in a structure The polymer structure can include any useful combination having formula ( IIr ) ) . of substitutions , including one or more RM substituents in

In other embodiments , the AK alkyl - containing RH sub combination with one or more Rl and / or R3 substituents . For stituent is — 14 — AKA , in which LH is a carbonyl group and 30 instance , as seen in FIG . 4C , the polymer of structure ( II - 4 ) in which AK " is a halo - substituted alkyl group ( e . g . , per includes four R substituents ( e . g . , - C ( O ) - ( P - RA ! ) - Ph fluoroalkyl , — ( CF2 ) hiF , — ( CH2 ) hiF , or ( CHF ) n?f , in located on pendent aryl groups ) , a R ' substituent ( e . g . , which h1 is an integer of from about 1 to about 24 ) . As seen SO2H located on a backbone aryl group ) , and two Rº in FIG . 9 , exemplary polymers include structures having substituents ( e . g . , — SO3H located on pendent aryl groups ) . formula ( II - 11 ) or structures having formula ( II - 12 ) . 35 Any useful number and type of RH , R ' , and / or R3 substitu

Exemplary linkers L include a covalent bond , carbonyl ents can be present on a particular polymer structure . In IC ( O ) ) , oxy ( 0 ) , phosphonoyl ( P ( OH — ) , another instance , the number qofR ' substituent ( s ) is of from phosphoryl ( P ( O ) < ) , sulfonyl ( S ( O ) 2 — ) , sulfinyl ( S 0 to 5 for each aryl group ( e . g . , from 0 to 1 , 1 to 5 , 1 to 4 , ( 0 ) - ) , sulfonamide ( e . g . , — SO , — NR 3 — or — NR 3 — 1 to 3 , 1 to 2 , 2 to 5 , 2 to 4 , or 2 to 3 ) . SO2 - , where R13 is H , optionally substituted alkyl , option - 40 In one instance , the number h of RH substituent ( s ) is of ally substituted haloalkyl , optionally substituted alkoxy , from 0 to 5 for each aryl group ( e . g . , from 0 to 4 , 0 to 3 , 0 optionally substituted alkaryl , optionally substituted aryl , or to 2 , 0 to 1 , to 5 , 1 to 4 , 1 to 3 , 1 to 2 , 2 to 5 , 2 to 4 , or 2 halo ) , imino ( NH4 ) , imine ( e . g . , - CR = N — , where to 3 ) . In some embodiments , each aryl group includes one or R is H or optionally substituted alkyl ) , phosphine ( e . g . , more RH . In other embodiments , one aryl group includes one - PR23 — group , where RL3 is H or optionally substituted 45 or more RH . In other embodiments , each pendent aryl group alkyl ) , nitrilo ( e . g . , - NR - 3 — , where R 3 is H , optionally includes one or more RH . In yet other embodiments , one to substituted alkyl , optionally substituted haloalkyl , optionally three pendent aryl groups includes one or more RH . substituted alkoxy , optionally substituted alkaryl , optionally In other embodiments , each backbone aryl group or Art substituted aryl , or halo ) , optionally substituted C - 12 alky - aryl group includes one or more RH . In some embodiments , lene ( e . g . , ( CR R22 ) la — , where each of R1 and R22 is , 50 one backbone aryl group includes one or more RH . In independently , H , optionally substituted alkyl , optionally particular embodiments , each h for each aryl group is the substituted haloalkyl , optionally substituted alkoxy , option - same or different . ally substituted alkaryl , optionally substituted aryl , or halo ) , In another instance , each backbone aryl group or Art aryl optionally substituted C1 - 12 alkyleneoxy , optionally substi - group includes one or more R ! . In particular embodiments , tuted C1 - 12 heteroalkylene ( e . g . , - C ( O ) NR23 — , - NR23C 55 each q for each aryl group is the same or different . In yet ( 0 ) — , ( CRLIRL2 ) C ( O ) - NR23 — , - ( CRLIRI ? ) . another instance , the number ofRº substituent ( s ) is of from NR23 _ C ( O ) - , ( CRLIR22 ) La S02 - NR 3 , or 0 to 5 for each aryl group ( e . g . , from 0 to 1 , 1 to 5 , 1 to 4 , - SO2 - NR23 — ( CRIRE2 ) — , where each of R1 , R22 , and 1 to 3 , 1 to 2 , 2 to 5 , 2 to 4 , or 2 to 3 ) . In some embodiments , RL is , independently , H , optionally substituted alkyl , option - each pendent aryl group includes one or more R3 . ally substituted haloalkyl , optionally substituted alkoxy , 60 Any useful RA substituents can be present on any number optionally substituted alkaryl , optionally substituted aryl , or of aryl groups ( e . g . , some of the pendent aryl groups , such halo ) , optionally substituted C1 - 12 heteroalkyleneoxy , as of from about 1 to about 3 pendent aryl groups ) . For optionally substituted C4 - 18 arylene , or optionally substi - instance , FIG . 5A provides another polymer of structure tuted C4 - 18 aryleneoxy . ( II - 5 ) , which includes three pendent aryl groups ( i . e . , pen

Further exemplary reactive handles RH include - C ( O ) - 65 dent aryl groups Ar1 , Ar4 , and Ar6 ) and in which each of Arh , in which Art is an optionally substituted aryl ( e . g . , these pendent groups includes a RH substituent of - C ( O ) optionally substituted phenyl with one or more optional ( R $ ) s - Ph . In another instance , FIG . 5B provides another

US 10 , 053 , 534 B2 27 28

polymer of structure ( II - 6 ) , which includes three pendent optionally substituted C4 - 18 aryloxy , hydroxyl , or H ) , sub aryl groups ( i . e . , pendent aryl groups Arl , Art , and Arb ) and stituted phosphonoyl ( e . g . , — P ( O ) HRPI , where RP is in which each of these pendent groups includes a R optionally substituted C1 - 12 alkyl , optionally substituted substituent of — S02 — ( RHI ) s - Ph . C1 - 12 alkoxy , optionally substituted C4 - 18 aryl , optionally

Other exemplary reactive handles R " include SO2 — 5 substituted C . , alk - C21e aryl , optionally substituted C218 Art , in which Art is an optionally substituted aryl ( e . g . , aryloxy , hydroxyl , or H ) , alkylphosphorylalkyl ( e . g . , optionally substituted phenyl with one or more optional RP4P ( O ) < RAIRP2 , where RPA is optionally substituted substituents selected from the group of halo , haloalkyl , nitro , C1 - 12 alkylene or optionally substituted heteroalkylene ; and nitroso , alkoxy , etc . ) . In another instance , RM includes - SO , each of RP and RP2 is , independently , optionally substituted Ph , in which Ph is substituted with h1 number of RH1 , where 10 RAl is selected from the group of halo , haloalkyl , nitro , C1 - 12 alkyl , optionally substituted C1 - 12 alkoxy , optionally

substituted C4 - 18 aryl , optionally substituted C1 - 12 alk - C4 - 18 nitroso , alkoxy , etc . , and where h1 is an integer of from 1 to 5 ) . aryl , optionally substituted C4 - 18 aryloxy , hydroxyl , or H ) ,

Exemplary acidic moieties ( e . g . , R ' ) include any group arylphosphoryl ( e . g . , P ( O ) < R4 ' RP2 or — P ( O ) < R4 ' R4 " , where each Rar is , independently , optionally substituted having one or more sulfonyl groups , such as sulfo ( e . g . , 15

- S02OH ) , alkylsulfonyl ( e . g . , S02 RSI , where RSI C4 - 18 aryl , optionally substituted C1 - 12 alk - C4 - 18 aryl , or is optionally substituted C1 - 12 alkyl ) , alkylsulfonylalkyl optionally substituted C4 - 18 aryloxy ; and RP2 is optionally ( e . g . , - R $ 4 _ SO , RSI , where each of RSA is optionally substituted C1 - 12 alkyl , optionally substituted C1 - 12 alkoxy , substituted C1 - 12 alkylene or optionally substituted het optionally substituted C4 - 18 aryl , optionally substituted C1 - 12 eroalkylene and RSI is optionally substituted C1 - 12 alkyl ) , 20 alk - C4 - 18 aryl , optionally substituted C4 - 18 aryloxy , arylsulfonyl ( e . g . , SO2 - R4r , where R4 " is optionally hydroxyl , or H ) , or arylphosphorylalkyl ( e . g . , RP4 — substituted C4 - 18 aryl ) , arylsulfonylalkyl ( e . g . , RS4 — P ( O ) < R4 ' RP2 or - RPA — P ( O ) < R4 R4r , where RPA is , inde SO2 - R4r , where RSA is independently , optionally substi pendently , optionally substituted C1 - 12 alkylene or option tuted C1 - 12 alkyl or alkylene and R4 ” is optionally substituted ally substituted heteroalkylene ; each R4 " is , independently , C4 - 18 aryl ) , sulfonamoyl ( e . g . , SO NRWR ̂ 2 ) , sulfoamino 25 optionally substituted C4 - 18 aryl , optionally substituted C1 - 12 ( e . g . , - N ( RM ) S02 R $ ) , aminosulfonyl ( e . g . , S02 — alk - C4 - 18 aryl , or optionally substituted C4 - 18 aryloxy ; and NRM _ R $ 2 ) , or sulfonyl imide ( e . g . , SO2 - NRM — RP2 is optionally substituted C1 - 12 alkyl , optionally substi SO2 R $ 3 ) , where each of RM and RN2 is , independently , H , tuted C1 - 12 alkoxy , optionally substituted C4 - 18 aryl , option optionally substituted C1 - 12 alkyl ( e . g . , haloalkyl , such as ally substituted C1 - 12 alk - C4 - 18 aryl , optionally substituted perfluoroalkyl ) , optionally substituted C4 - 18 aryl , or option - 30 C4 - 18 aryloxy , hydroxyl , or H ) , where each of these groups ally substituted C1 - 12 alk - C4 - 18 aryl ; RS2 is H , optionally can be optionally substituted ( e . g . , with one or more sub substituted C1 - 12 alkyl ( e . g . , haloalkyl , such as perfluoro - stituents described for alkyl , as defined herein ) . alkyl ) , hydroxyl , optionally substituted C - 12 alkylsulfonyl , In any of these moieties , each of RPI and RP2 is , inde optionally substituted C4 - 18 aryl , or optionally substituted pendently , optionally substituted C1 - 12 alkyl ( e . g . , haloalkyl , C1 - 12 alk - C4 - 18 aryl ; and R $ 3 is H , hydroxyl , optionally 35 such as C1 - 12 perfluoroalkyl ) , optionally substituted C1 - 12 substituted C1 - 12 alkyl ( e . g . , haloalkyl , such as perfluoro alkoxy , optionally substituted C4 - 18 aryl , optionally substi alkyl ) , optionally substituted C4 - 18 aryl , or optionally sub tuted C1 - 12 alk - C4 - 18 aryl , optionally substituted C4 - 18 ary stituted C1 - 12 alk - C4 - 18 aryl . loxy , hydroxyl , or H ; each of R4r is , independently , option

In any of these moieties , each RSI and R $ 3 is , indepen - ally substituted C4 - 18 aryl , optionally substituted C1 - 12 alk dently , optionally substituted C1 - 12 alkyl ( e . g . , haloalkyl , 40 C4 - 18 aryl , or optionally substituted C4 - 18 aryloxy ; and each such as C1 - 12 perfluoroalkyl ) , optionally substituted C1 - 12 RPA is , independently , oxy , optionally substituted C1 - 12 alky alkoxy , optionally substituted C4 - 18 aryl , optionally substi lene , or optionally substituted heteroalkylene . tuted C1 - 12 alk - C4 - 18 aryl optionally substituted C4 - 18 ary - Yet other exemplary acidic moieties ( e . g . , Rº ) include any loxy , hydroxyl , or H ; each RS2 is independently , optionally group having a carbonyl group , such as carboxyl ( e . g . , substituted C1 - 12 alkyl ( e . g . , haloalkyl , such as perfluoro - 45 CO2H ) , C ( O ) - Rºi , or RCA - C ( O ) - RC ( e . g . , alkyl ) , optionally substituted C1 - 12 alkylsulfonyl , optionally where each RCI is , independently , optionally substituted substituted C1 - 12 alkoxy , optionally substituted C4 - 18 aryl , C1 - 12 alkyl ( e . g . , haloalkyl , such as C1 - 12 perfluoroalkyl ) , optionally substituted C1 - 12 alk - C4 - 18 aryl optionally substi optionally substituted C1 - 12 alkoxy , optionally substituted tuted C4 - 18 aryloxy , hydroxyl , or H ; each R4r is , indepen C4 - 18 aryl , optionally substituted C1 - 12 alk - C4 - 18 aryl , option dently , optionally substituted C4 - 18 aryl , optionally substi - 50 ally substituted C4 - 18 aryloxy , hydroxyl , or H ; and each RCA tuted C1 - 12 alk - C4 - 18 aryl , or optionally substituted C4 - 18 is , independently , oxy , optionally substituted C1 - 12 alkylene , aryloxy ; each of RSA is , independently , oxy , optionally or optionally substituted heteroalkylene ) . substituted C1 - 12 alkylene , or optionally substituted het . Exemplary electron - withdrawing moieties ( e . g . , R " ) eroalkylene ; and each of RM and RN2 is , independently , H , include optionally substituted C7 - 11 aryloyl , optionally sub optionally substituted C1 - 12 alkyl ( e . g . , haloalkyl , such as 55 stituted C6 - 18 aryl , carboxyaldehyde , optionally substituted perfluoroalkyl ) , optionally substituted C4 - 18 aryl , or option - C2 - 7 alkanoyl , optionally substituted C1 - 12 alkyl , optionally ally substituted C1 - 12 alk - C4 - 18 aryl . substituted C1 - 12 haloalkyl , optionally substituted C2 - 7

Other exemplary acidic moieties ( e . g . , R ' ) include any alkoxycarbonyl , nitro , nitroso , cyano , sulfo , carboxyl , and group having one or more phosphoryl groups , such as quaternary ammonium ( e . g . , — N + RMRM2RN3 , where each phosphono ( e . g . , — P ( O ) ( OH ) 2 ) , phosphoric ester ( e . g . , 60 of RM , RN2 , and RN3 is , independently , optionally substi - O - PO ( OH ) 2 or0 P ( O ) < RPIRP2 or 0 P ( O ) tuted alkyl , optionally substituted alkaryl , or optionally

RAIRP2 or 0 — P ( O ) < R4PR4r , where each R4 " is the same substituted aryl , or two of RM , RN2 , and RN3 , taken together or different ) , alkylphosphoryl ( e . g . , — P ( O ) < RPRP , where with the nitrogen atom to which each are attached , form a RP is optionally substituted C1 - 12 alkyl or optionally sub heterocyclyl group , as defined herein ) . In another embodi stituted C1 - 12 alkoxy ; and RP2 is optionally substituted C1 - 12 65 ment , R? includes or is substituted by a C1 - 12 perfluoroalkyl alkyl , optionally substituted C1 - 12 alkoxy , optionally substi group . In yet another embodiment , R? is a C1 - 12 perfluoro tuted C4 - 18 aryl , optionally substituted C - 12 alk - C4 - 18 aryl , alkyl group .

US 10 , 053 , 534 B2 29 30

- continued

N

15

One or more functional groups R4 can be appended to a reactive handle RH . Exemplary functional groups ( e . g . , R4 ) include any useful group , such as halo , nitro , nitroso , cyano , amino , amido , optionally substituted C1 - 12 alkyl , optionally substituted C1 - 12 haloalkyl , optionally substituted C1 - 12 per - 5 fluoroalkyl , optionally substituted C1 - 12 heteroalkyl , option ally substituted C1 - 12 alkoxy , optionally substituted aryl , optionally substituted alkaryl , optionally substituted arylal koxy , optionally substituted aryloxy , optionally substituted aryloxycarbonyl , optionally substituted aryloyl , optionally 10 substituted arylsulfonyl , and optionally substituted arylsul fonylalkyl . FIG . 7 provides a structure having the formula ( VI ) having h * number of RH * substituents , in which RH * includes a number a of reacted reactive handle RH ( e . g . , a reactive handle R " , such as any herein , lacking a leaving group ( e . g . , H , halo , etc . ) ) that is covalently bonded to a functional group R4 and includes a number h - a of non reacted reactive handle RH , and in which ash . Any number of RH substituents can include a functional group R4 . In one 20 instance , every RH is reacted with one or more R4 , thereby providing a h * number of RA * and in which h * is h ) . In another instance , some RH is reacted with one or more R4 , thereby providing a h * number of RH * and in which h * = a < h .

The reactive handles , acidic moieties , electron - withdraw ing moieties , and / or functional groups can be substituted or unsubstituted . For example , these groups can be substituted with one or more substitution groups , as described herein for alkyl and / or aryl .

Aryl Groups The aryl groups herein can have any useful configuration ,

structure , and substitutions . Exemplary aryl groups ( e . g . , including arylene groups , such as for Art , Ar , and Ar * ) include the following groups , which may be optionally substituted :

30

- 35

40

- * - oooo 45 – z

and

45 - - 2 - - 2

ca where each of Z , Z ' , z ? , and Z is , independently , 0 ,

50 S - , - S02 - , optionally substituted C1 - 12 alkylene , optionally substituted C1 - 12 alkyleneoxy , optionally substi tuted C1 - 12 heteroalkylene , optionally substituted C1 - 12 het eroalkyleneoxy , CF2 — , - CH2 - , - OCF2 — , perfluoro alkylene , perfluoroalkyleneoxy , Si ( Rº ) 2 - , - P ( O ) ( R ) — , - PR - , - C ( O ) - , - C ( CF3 ) 2 - , - C ( CH3 ) 2 - , or CCF3Ph - , and where R ' is H , optionally substituted alkyl ,

or optionally substituted aryl ( e . g . , methyl , ethyl , isopropyl , t - butyl , or phenyl ) .

60 Polymer Salts The present invention includes a salt of any polymer

described herein , e . g . , a salt of any one of formulas ( II ) , ( IHa ) , ( IIb ) , ( IIC ) , ( IId ) , ( Ile ) , ( IIf ) , ( Hg ) , ( IIh ) , ( IIi ) , ( Ilj ) , ( Ilk ) , ( III ) , ( IIm ) , ( IIn ) , ( c ) , ( IIp ) , ( Ilq ) , ( IIr ) , ( III ) , ( IIIa ) ,

65 ( IIIb ) , ( IIIc ) , ( IIId ) , ( IV ) , ( V ) , ( Va ) , and ( VI ) , as well as particular structures provided as structures ( II - 1 ) , ( II - 2 ) , ( II - 3 ) , ( II - 4 ) , ( II - 5 ) , ( II - 6 ) , ( II - 7 ) , ( II - 8 ) , ( II - 9 ) , ( II - 10 ) , ( II

32

( 2 )

US 10 , 053 , 534 B2 31

11 ) , ( II - 12 ) , ( II - 13 ) , ( II - 14 ) , ( II - 15 ) , ( II - 16 ) , ( II - 17 ) , and halo , hydroxyl , or sulfonate , such as mesylate , tosylate , or ( II - 18 ) . In particular embodiments , the salt is a sodium salt . triflate ) and RA is any described herein ( e . g . , RH can be Methods of Making Polymer Structures - LH — ANH or LH - AKH ) . The polymers of the invention can be synthesized using The concentration of RH — X can be controlled to provide

any useful scheme . The following synthetic schemes are 5 the desired extent of substitution on the DAPP pendent provided as non - limiting examples . and / or backbone aryl groups . As can be seen , the number of

RA substituents h on each aryl group can be controlled by the stoichiometry of reagent RA — X and ( DAPP ) ( 3 ) . In one

Scheme I instance , concentration can be controlled in order to install 10 RA substituents on readily accessible pendent aryl groups .

The reaction can be conducted until completion in order to access the backbone aryl groups , which are sterically more

— Ap = difficult to functionalize . Optionally , the substitution reaction with reagent RH — X

15 is performed in the presence of a metal salt and / or in the ( - 2 CO ) presence of an acid . Exemplary metal salts include M [ O ( SO2 - RMF ) ] , M [ N ( SO2 - RM " ) 2 ] , or M [ C ( SO2 - RM ) 3 ] , where R * is optionally substituted alkyl , optionally substi tuted aryl , optionally substituted alkaryl , optionally substi

20 tuted haloalkyl , or perfluoroalkyl , and where M is Ag , A1 , Ba , Bi , Ca , Cu , In , Re , Sc , Sn , Ti , Y , Yb , or Zn . Particular embodiments of metal salts include M [ OTf ] me where mf is an integer from 1 to 3 and where M is Ag , Al , Ba , Bi , Ca , Cu , In , Sc , Y , or Yb ; as well as M [ NTflmt where mf is an

metal salt / acid catalyst 25 integer from 1 to 3 and where M is Ag , Al , Sn , Ti , Yb , or Zn . RH - X Exemplary acids include a Lewis acid or a Bronsted acid

( e . g . , ApH - LH - X or that acts as a catalyst , such as , e . g . , HO ( SO2 - RA ) , AkH — 14 - X , HO ( SO2 - R4 ) , HO ( SO , F ) , HO ( SO2 - R4 " ) , and HO ( C where ( 0 ) - RA ) , where RAF is optionally substituted alkyl ,

RH = Ar — IH or Ar 1 " or 30 optionally substituted aryl , optionally substituted alkaryl , RH = AKH - LH ) optionally substituted haloalkyl , or perfluoroalkyl , and

where R4r is optionally substituted aryl or optionally sub ( RH ) n ( RH ) n ( RH ) ( RM ( RH ) ( RM ) stituted alkaryl . Particular embodiments of acids include HO ( SO2CF3 ) , HO ( SOF ) , H2SO4 , HO ( SO2 - ( P - CH3 ) Ph ) , or

35 HO ( COCF3 ) .

- 171

( 3 )

Scheme II ( RA )

— AM ( 2 )

( - 2 CO ) 45 4 ) m 1 .

( RM ) ( R )

( III )

50

R3 - X 4 .

( e . g . , R3 ' ' x g

- 1

As shown in Scheme I , the polymer of formula ( Ili ) can be formed by performing a Diels - Alder reaction to form the pendent and backbone aryl groups , and then performing a first substitution reaction to introduce RH to the parent structure . These two steps are described in more detail 55 below .

First , a Diels - Alder reaction can be performed with an optionally substituted diene , such as a 1 , 4 - bis - ( 2 , 4 , 5 - triph enylcyclopentadienone ) arylene reagent ( 1 ) , with an option ally substituted dienophile , such as a diethynylarylene 60 reagent ( 2 ) . This reaction provides a Diels - Alder poly ( phe nylene ) polymer ( DAPP ) ( 3 ) . As can be seen , in this step , the number of subunits m is controlled by the stoichiometry of reagents ( 1 ) and ( 2 ) .

Second , a substitution reaction is performed with reagent 65 RH — X with the DAPP product ( 3 ) to provide a substituted polymer ( Ili ) , where X is any useful leaving group ( e . g . ,

= o

RSI — 5 — X , o =

where R3 = R3 ' — C —

or

RSI - S ( O ) 2 - )

34

com resta che ( R3

port ) , s Or O

- 111 = ( R )

O

or

GR ) ( R3 ) AN

( R ) or

RO Im ( R ) , 171 L or

N 30 30

( R ? ) ( R ) ,

US 10 , 053 , 534 B2 33

- continued The third step includes a second substitution reaction , which is performed with reagent R - X in the presence of

/ H - ( R3 ( R3 ) RI - X the substituted polymer ( 4 ) to provide the desired polymer of ( when Ri is not H ) 5 formula ( I ) . For reagent R - X , X is any useful leaving group ( e . g . , halo , hydroxyl , or sulfonate , such as mesylate ,

( e . g . , R1x tosylate , or triflate ) , and R ' is any described herein . * ( R ' ) a Finally , the fourth step includes a third substitution reac

RSI - S - X , 10 tion , which is performed with reagent RH - X in the pres where ence of the DAPP product ( 3 ) to provide a substituted

Ri = RI - C ( O ) polymer ( II ) . For reagent RH — X , X is any useful leaving RSI - S ( O ) 2 - ) group ( e . g . , halo , hydroxyl , or sulfonate , such as mesylate ,

15 tosylate , or triflate ) , and RH is any described herein ( e . g . , RH can be [ 4 – Ary or - 14 — AKA ) . metal salt / acid

catalyst The three substitution steps ( i . e . , the second , third , and RH - X fourth steps ) can be performed in any order to obtain the ( e . g . , ApH - LH - X 20 desired substitution pattern . Of course , if R3 and R are the AkH - LH - X , same substituents , then only one of the substitution reaction

where ( R3 ) steps can be conducted . Alternatively , one or more steps may RH = ApH - LH be required to install R or R3 on the parent molecule . For

instance , when Rl or R3 is SO , NRM RS2 , multiple ( where Art = Ar — ( R ) , for RH = AkH – 1H ) 25 steps may be required to first install the SO2 - functional this non - limiting instance ) group on the parent molecule . Then , this functional group ( R?A ( RFA ( RHA ( RH ) 4 ( R " h ( RA may be activated ( e . g . , by forming a sulfonyl halide , such as Fa sulfonyl chloride ) and reacted with an amine ( e . g . ,

NHRN R ? ) . ( R ) , I In another instance , an additional step may be required to

( R ) ? ( R ) install the - RS2 functional group . For example , when R ' or R3 includes two sulfonyl groups , such as in SO2 ( RM ) NRM _ S02 RS2 ' , then then sulfonyl groups can be attached sequentially . In one example , the method includes installing the first - S0 - functional group on the parent molecule and then reacted with a primary amine , such as NH , RM , thereby providing a parent molecule having a

( RP ) L = _ ( R ) - S02 NHRM sulfonamide group . This sulfonamide can 40 then be reacted with an activated sulfonyl agent , e . g . , a

Cl - S02 RS2 ' agent , where RS2 ' is an optionally substituted C1 - 12 alkyl , thereby providing an RS moiety of s02 NRNI _ SO2 - RS2 on the polymer .

As shown in Scheme II , the polymer of formula ( II ) can 16 In yet another instance , when Rl or R3 is RP4 — P ( O ) < be formed by performing a Diels - Alder reaction to form the RPIRP2 , multiple steps may be required to first install the pendent and backbone aryl groups , performing a first sub - R ' A alkylene or heteroalkylene on the parent molecule , and stitution reaction to introduce R3 to the parent structure , then to later install the — P ( O ) < RPIRP2 group on the alky

lene or heteroalkylene molecule . Furthermore , if Rpl or RP2 performing a second substitution reaction to introduce R ' , ? 50 is an alkoxy or aryloxy group , then additional step may be and performing a final substitution reaction to introduce RH . 50 required to modify a hydroxyl group attached to the phos These four steps are described in more detail below . phorous atom with an alkoxy or aryloxy group . A skilled Similar to Scheme I , the first step in Scheme II includes artisan would understand that additional modifications or

a Diels - Alder reaction that is performed with an optionally step can be employed to arrive at the desired structure . substituted diene , such as a 1 , 4 - bis - ( 2 , 4 , 5 - triphenyl cyclo - 55 Exemplary R ? — X and R3 - X reagents include HSOZCI , pentadienone Jarylene reagent ( 1 ) , in the presence of an H2SO4 , PC13 , POC13 , H3PO4 , SO3 , fuming sulfuric acid , optionally substituted dienophile , such as a diethynylarylene thionyl chloride , trimethylsilyl chlorosulfonate , dialkyl

phosphites ( e . g . , diethyl phosphate with an optional catalyst , reagent ( 2 ) . This reaction provides a Diels - Alder poly ( phe such as a Pd ( 0 ) catalyst ) , phosphines ( e . g . , tertiary phos nylene ) polymer ( DAPP ) ( 3 ) . 60 phines ) , phosphoric acids ( e . g . , hypophosphorous acids ,

The second step includes an initial substitution reaction , phosphonic acids , phosphinic acids , etc . ) , aryl halide ( e . g . , which is performed with reagent R3X in the presence of RX , where R is an optionally substituted aryl group , as the DAPP product ( 3 ) , thereby providing a substituted defined herein , and X is halo ) , aryl halide ( e . g . , RX , where

R is an optionally substituted aryloyl group , as defined polymer ( 4 ) . For reagent R X , X is any useful leaving 65 herein , and x is halo , such as trifluorobenzoyl chloride ) . group ( e . g . , halo , hydroxyl , or sulfonate , such as mesylate , protein kinase ( e . g . , to install a phosphoryl group ) , phospho tosylate , or triflate ) and R is any described herein . noxyphenols , as well as mixtures thereof .

E

35

( R ' )

( R ' a

( RA ) DH ( R4 ( R ( II )

35 US 10 , 053 , 534 B2

36 - continued

( RH ) n ( RH ) n ( RH ) in ( RH ) n ( RM ) n ( RH ) n Ela | T Fla

Scheme III

R3 _ AX ( R3 ) ( R ) ( R ! ) . ( R )

- ApM - Apl ( RH ) ( 2 )

( - 2 CO ) 10 Art ( R )

R ) , X L ( R ) ( RH ) n 1 ( RH ) R4 , ( R ̂

( II ) ( where Art = Ap — ( R ' ) , for

this non - limiting instance ) metal Lewis acid

catalyst RH - X

( e . g . , ApH - LH - X 20

or AKH - LH - X ,

where RH = AH - LH

or RH = AKH – LH

( RFA ( RFA ( RF ) ( RHA ( RPA ( RFA

R - X 0

— A * Am ( e . g . , R3 " x c . g . , R3 '

? O =

RSI - S - X , m ( RM ) = 0

( RM ) where R3 = R3 - C ( 0 ) —

As discussed herein , the substitution steps can be per formed in any useful order . In one non - limiting instance , the

35 reaction scheme includes introducing one or more reactive handles R " , and then introducing other substitution groups ( e . g . , R and / or Rº ) . As shown in Scheme III , the polymer of formula ( II ) can be formed by performing a Diels - Alder reaction to form the pendent and backbone aryl groups , performing a first substitution reaction to introduce RH , performing a second substitution reaction to introduce Rºto the parent structure , and performing a final substitution

35 reaction1 10 m 35 reaction to introduce R . In one instance , the substitution steps including R3 and R ' can be conducted in the opposite order . These four steps are described in more detail below .

Similar to Schemes I and II , the first step in Scheme III 10 includes a Diels - Alder reaction that is performed with an

optionally substituted diene , such as a 1 , 4 - bis - ( 2 , 4 , 5 - triph enyl cyclopentadienone ) arylene reagent ( 1 ) , in the presence of an optionally substituted dienophile , such as a diethy nylarylene reagent ( 2 ) . This reaction provides a Diels - Alder

45 poly ( phenylene ) polymer ( DAPP ) ( 3 ) . The second step includes a first substitution reaction ,

which is performed with reagent RH — X in the presence of the DAPP product ( 3 ) to provide a R4 - substituted polymer ( 5 ) . For reagent RH — X , X is any useful leaving group ( e . g . ,

W halo , hydroxyl , or sulfonate , such as mesylate , tosylate , or triflate ) , and RH is any described herein ( e . g . , R can be LH - APH or — LH - AKH ) . The third step includes a second substitution reaction ,

55 which is performed with reagent R3 - X in the presence of the RH - substituted polymer ( 5 ) , thereby providing a RH — , Rº - substituted polymer ( 6 ) . For reagent R - X , X is any useful leaving group ( e . g . , halo , hydroxyl , or sulfonate , such as mesylate , tosylate , or triflate ) and R is any described

60 herein . Finally , the fourth step includes a third substitution reac

tion , which is performed with reagent R - X in the presence of the RH , R3 - substituted polymer ( 6 ) to provide the desired polymer of formula ( II ) . For reagent R ? — X , X is any

65 useful leaving group ( e . g . , halo , hydroxyl , or sulfonate , such as mesylate , tosylate , or triflate ) , and R ' is any described herein .

RSI - S ( O ) 2 - )

( RFA ( RF ) ( Rºa ( RF ) ( R " h ( RPM

( R31 _ ( R3 ) la - - LA ( R ) ( RS ) ( RH ) , R ! - X

( when Ri is not H )

( e . g . , R1 x ( R ) , XLR ( RH ( RH ) ( RM )

or

RSI - S - X , ( 6 ) where

R = R ' - C ( O ) or

RSI - S ( O ) 2 - )

US 10 , 053 , 534 B2 37 38

Scheme IV - continued

( RH ) n ( RH ) n ( R ) ( RH ) n ( RH ) n ( RH ) n Pahalah F =

= = LA ( R3 ) = = AM

( 2 ) RE

( RA ) L

( 7 ) ALM7 R / ( R ' ) ( R ! ) L - R2

( R ) , X - LXR3 ) . ( RH ) n ( RH ) , ( RM )

( III ) ( where Ar = Ap — ( R ! ) , for

this non - limiting instance )

AN 25 | L ' = L =

Art R3 - X 1 AM

L ' - R2 30

292 ( R )

ne 45

L ' - RC

/ ( Rº ) L ( R3 ) O

As shown in Scheme IV , the polymer reagent of formula ( III ) can be formed by performing a Diels - Alder reaction to form the pendent and backbone aryl groups and to install reactive end groups R ' . Then , substitution reactions can be

35 performed in order to introduce R ’ , R ' , and / or RH . These three steps are described in more detail below .

Similar to that of Scheme I , the first segment is formed by performing a Diels - Alder reaction with a 1 , 4 - bis - ( 2 , 4 , 5 triphenylcyclopentadienone arylene reagent ( 1 ) and a

10 diethynylarylene reagent ( 2 ) . To further install reactive end groups , the Diels - Alder

reaction is also performed in the presence of a monoethy nylarylene reagent ( 7 ) . As can be seen , because reagent ( 2 ) includes two dienophile groups ( i . e . , two ethynyl groups ) , this reagent can react with two diene molecules ( 1 ) , where the product of this reaction can further propagate the polym erization reaction . In contrast , reagent ( 7 ) includes only one dienophile group , and therefore terminates the polymeriza tion reaction and provides a polymer reagent ( 8 ) having a terminal reactive end group R ' . Additional methods for

50 installing reactive end groups are described in U . S . Pat . No . 8 , 110 , 636 , which is incorporated herein by reference in its entirety .

Then , substitution reaction ( s ) can be performed . In Scheme IV , the substitution reactions are provided as three

55 steps performed first with reagent R3 _ X ( e . g . , as described herein ) in the presence of an unsubstituted polymer ( 8 ) to form a further polymer ( 9 ) , then with reagent R - X ( e . g . , as described herein ) to form a further polymer ( 10 ) , and finally with reagent RH — X ( e . g . , as described herein ) to

60 form polymer reagent ( III ) . If R and R are the same substituents , then a single substitution reaction step can be conducted . If R² and Rl are different , then these substituents can be added in any desired order . A skilled artisan would understand that other modifications could be made to form

65 the desired polymer reagent ( III ) . In exemplary Scheme ( IV ) , Are in formula ( III ) is Art ' — ( R1 ) ? , which is a non limiting embodiment .

( R ” Ja metal

LABAM ] salt / acid catalyst

RH - X RT RK R La This ( R ' ) L ' - RL

( R ? .

( 10 )

US 10 , 053 , 534 B2 39 40

Methods of making the polymer also include preparing an 2001 ; 57 : 241 - 7 , Effenberger F et al . , “ Trifluoromethanesul initial polymer having one or more RP and / or Rº substitu fonic - carboxylic anhydrides , highly active acylation ents , and then installing one or more R on one or more agents , ” Angew . Chem . Int ' l Ed . 1972 ; 11 ( 4 ) : 299 - 300 , pendent and / or backbone aryl groups . As seen in FIG . 8A , Effenberger F et al . , " Catalytic Friedel - Crafts acylation of in one instance , the initial polymer is a sulfonated DAPP 5 aromatic compounds , ” Angew . Chem . Int ' l Ed . 1972 ; 11 ( 4 ) : polymer ( SDAPP ) having one or more sulfo groups ( e . g . , on 300 - 1 , and Rakira P E , “ Triflic acid and its derivatives : a one or more pendent aryl groups ) , which can then be reacted family of useful reagents for synthesis , ” Chem . Today 2004 with reagent RA — X to install one or more RA substituents May / April : 48 - 50 , as well as U . S . Pat . Nos . 8 , 809 , 483 , on that SDAPP polymer . As also seen in FIG . 8A , in another 8 , 110 , 636 and 7 , 301 , 002 , each of which is incorporated instance , the initial polymer is a fully sulfonated DAPP 10 herein by reference in its entirety . polymer ( FS - DAPP ) having one or more sulfo groups ( e . g . , Uses on one or more pendent aryl groups and on one or more The polymers of the invention can be used in a variety of backbone aryl groups ) , which can then be reacted with electrochemical applications . For instance , any polymer reagent RH — X to install one or more RH substituents on that herein can be prepared as a membrane ( e . g . , by casting ) , and FS - DAPP polymer . 15 the membrane ( e . g . , a proton exchange membrane ) can be

In another instance , a precursor of the polymer herein incorporated into any device . In another instance , a precur ( e . g . , a polymer having a structure of formula ( I ) ) is prepared sor of the polymer herein ( e . g . , a polymer having a structure as a membrane , and further functionalization is conducted to of formula ( I ) ) is prepared as a membrane , and further include one or more RH , R ' , and / or R $ substituents by functionalization is conducted to include one or more RH , reacting the membrane with one or more reagents to install 20 Rl , and / or R3 substituents by reacting the membrane with such substituents . one or more reagents to install such substituents . Any reactions herein can be conducted with any useful Exemplary devices include fuel cells ( e . g . , automotive

reagent , solvent , or conditions . An example of reagent ( 1 ) fuel cells , hydrogen fuel cells , or direct methanol fuel cells ) , includes 1 , 4 - bis - ( 2 , 4 , 5 - triphenylcyclopentadienone ) ben - flow batteries ( e . g . , redox flow batteries , such as vanadium zene , and an example of reagent ( 2 ) includes diethynylben - 25 redox flow batteries ) , electrolyzers , electrochemical hydro zene reagent . Exemplary solvents useful for Diels - Alder and gen production devices , etc . The membranes can be used for substitution reactions include an ether ( e . g . , diphenyl ether ) , any use , such as a proton exchange membrane , an ion methylene chloride , dichloroethane , etc . Salts of any poly - exchange resin , a polymer separator , etc . In addition , the mers can be obtained by reacting any product with a suitable membranes can be in any useful form , such as a hydrogel . acid or base to obtain the desired acid or base addition salt . 30 Membranes formed from the polymers herein can , in some Furthermore , additional reaction steps can be conducted to instances , display enhanced properties , such as enhanced ion further purify , test , or use any polymer herein . exchange capacity , decreased water uptake , and / or enhanced

Additional details on synthesis are described in Fujimoto durability ( e . g . , as determined by stress - strain measure C H et al . , “ Ionomeric poly ( phenylene ) prepared by Diels - ments ) . Methods of forming and testing membranes are Alder polymerization : Synthesis and physical properties of 35 described in Fujimoto C H et al . , Macromolecules 2005 ; a novel polyelectrolyte , " Macromolecules 2005 ; 38 : 5010 - 6 , 38 : 5010 - 6 , Lim Y et al . , Electrochim . Acta 2014 ; 119 : 16 - 23 , Lim Y et al . , “ Synthesis and properties of sulfonated poly Sun C - N et al . , “ Evaluation of Diels - Alder poly ( phenylene ) ( phenylene sulfone ) s without ether linkage by Diels - Alder anion exchange membranes in all - vanadium redox flow reaction for PEMFC application , ” Electrochim . Acta 2014 ; batteries , ” Electrochem . Commun . 2014 ; 43 : 63 - 6 , Merle G 119 : 16 - 23 , Hibbs MR et al . , “ Synthesis and characterization 40 et al . , “ Anion exchange membranes for alkaline fuel cells : A of poly ( phenylene ) - based anion exchange membranes for review , ” J . Membrane Sci . 2011 ; 377 : 1 - 35 , Stanis R J et al . , alkaline fuel cells , " Macromolecules 2009 ; 42 : 8316 - 21 , “ Evaluation of hydrogen and methanol fuel cell performance Jakoby K et al . , “ Palladium - catalyzed phosphonation of of sulfonated Diels Alder poly ( phenylene ) membranes , " J . polyphenylsulfone , ” Macromol . Chem . Phys . 2003 ; 204 : 61 - Power Sci . 2010 ; 195 : 104 - 10 , and Fujimoto C et al . , “ Vana 7 , Parcero E et al . , “ Phosphonated and sulfonated polyphe - 45 dium redox flow battery efficiency and durability studies of nylsulfone membranes for fuel cell application , ” J . Membr . sulfonated Diels Alder poly ( phenylene ) s , " Electrochem . Sci . 2006 ; 285 : 206 - 13 , Poppe D et al . , “ Carboxylated and Commun . 2012 ; 20 : 48 - 51 , as well as U . S . Pat . Nos . 8 , 809 , sulfonated poly ( arylene - co - arylene sulfone ) s : thermostable 483 , 8 , 110 , 636 , and 7 , 888 , 397 , each of which is incorpo polyelectrolytes for fuel cell applications , ” Macromolecules rated herein by reference in its entirety . 2002 ; 35 : 7936 - 41 , Akiko O at al . , “ Electrophilic aromatic 50 aroylation with CFz - bearing arenecarboxylic acid deriva EXAMPLES tives : Reaction behavior and acidic mediator dependence , " Synth . Commun . 2007 ; 37 : 2701 - 15 , Jang DO et al . , “ Highly Example 1 selective catalytic Friedel - Crafts acylation and sulfonylation of activated aromatic compounds using indium metal , ” 55 Functionalization of Diels - Alder Polyphenylene Tetrahedron Lett . 2006 ; 47 : 6063 - 6 , Skalski T J G et al . , Polymers “ Structurally - defined , sulfo - phenylated , oligophenylenes and polyphenylenes , ” J . Am . Chem . Soc . 2015 ; 137 ( 38 ) : Friedel - Crafts acylation reactions can be employed to 12223 - 6 , Kobayashi S et al . , “ Catalytic Friedel - Crafts acy - functionalize Diels - Alder polyphenylene polymers ( see , lation of benzene , chlorobenzene , and fluorobenzene using a 60 e . g . , U . S . Pat . No . 8 , 809 , 483 ) . As seen in FIG . 10A , a novel catalyst system , hafnium triflate and trifluorometh - Diels - Alder poly ( phenylene ) polymer ( DAPP ) is function anesulfonic acid , " Tetrahedron Lett . 1998 ; 39 : 4697 - 700 , alized by way of a Friedel - Crafts acylation reaction with an Noji M et al . , “ Secondary benzylation using benzyl alcohols alkyl acyl chloride ( e . g . , 6 - bromohexanoyl chloride ) in the catalyzed by lanthanoid , scandium , and hafnium triflate , ” J . presence of aluminum trichloride as a catalyst , thereby Org . Chem . 2003 ; 68 : 9340 - 7 , Singh R P et al . , “ An efficient 65 providing an alkyl acylated DAPP . method for aromatic Friedel - Crafts alkylation , acylation , When this Friedel - Crafts acylation approach was used to benzoylation , and sulfonylation reactions , ” Tetrahedron attach aryl acyl chlorides ( e . g . , benzoyl chloride ) , an

42 US 10 , 053 , 534 B2

41 insoluble product was obtained , which could not be pro - C . or greater , such as of from about 60° C . to about 140° C . ) ; cessed further ( FIG . 10B , top reaction pathway ) . Without solvent or solvent mixtures can be modified ( e . g . , by use of wishing to be limited by mechanism , Lewis acids , such as no solvent or by use of solvents with low donor numbers , FeClz and AIC1z , are known to catalyze oxidative carbon e . g . , ethers , acetone , aprotic solvents , non - polar solvents , carbon ( C — C ) coupling , including intramolecular and inter - 5 polar aprotic solvents , etc . ) ; and concentration of reactants molecular C — C coupling , as well as aryl - aryl coupling , can be altered to maximize yield and / or selectivity . such as in a Scholl reaction . Such coupling reactions are not The synthetic protocol is provided in FIG . 11A and was desired and may lead to insoluble polymeric products . Due conducted as follows . Two g of F - labeled DAPP ( 2 . 59 to the insolubility of the product provide by the reaction in mmol ) was dissolved in 20 mL of methylene chloride , and FIG . 10B ( top reaction pathway ) , we believe that only a 10 1 . 63 g of 4 - fluorobenzoyl chloride ( 10 . 3 mmol ) was added trace amount of intramolecular or intermolecular C - C to this yellow solution . The yellow solution was cooled in an coupling of pendent aryl groups in DAPP would result in coupling of pendent aryl groups in DAPP would result in ice bath , and 2 . 64 g of silver triflate ( 10 . 3 mmol ) was added insoluble cross linking . Common trace impurities in AIC1z , in one addition to give a dark brown color . After 1 hour , the such as FeCl2 and acidic protons , are potential catalysts for ice bath was removed ; and the reaction was stirred overnight this process . 15 at room temperature . Next day , the solution was added to

There are numerous differences between an alkyl acy water and heated to boil off the organic solvent . The remain lation reaction ( e . g . , as in FIG . 10A ) and an aryl acylation ing solid was then collected , rinsed with water several times , reaction ( e . g . , as in FIG . 10B ) . Without wishing to be limited and dried in a vacuum oven overnight at 60° C . by mechanism , the reaction pathway difference between The resultant product was dissolved in D - chloroform for alkyl and aryl acyl chlorides can be explained in terms of the 20 19F - NMR analysis to determine fluorine quantitative incor stability of the acylium ion intermediates . An aryl acylium poration ( FIG . 11B ) . The signal at - 105 ppm arose from the ion is stabilized by resonance delocalization , which is not pendent fluorine on the carbonyl aryl group , while the peak available in alkyl acylium . Thus , the alkyl acylium ion is at - 115 ppm corresponded to a backbone fluorine . Using the readily nucleophilically attacked by the pendent aryl groups peak at - 115 ppm as a reference signal , we estimated that of DAPP , while the aryl acylium ion reacts slower with the 25 about 2 . 6 pendent aryl fluorine groups were functionalized aryl groups so that it competes with aryl - aryl coupling ( see , per repeat group . e . g . , Corriu R et al . , “ Mécanisme de la C acylation : étude The aryl fluorine group can serve as a reactive handle , cinétique du mécanisme de l ' acétylation des composés aro which can be further reacted with other functional groups . In matiques catalysée par AlCl3 , ” Tetrahedron 1971 ; 27 : 5819 particular , the functional versatility of attaching the 4 - fluo 31 ; and Corriu R et al . , “ Mécanisme de la C acylation : étude 30 robenzoyl group is the lability of aryl halides in the presence cinétique du mécanisme de la benzoylation des composés of a strong electron withdrawing group towards nucleophilic aromatiques catalysée par AIC13 , ” Tetrahedron 1971 ; aromatic substitution ( SnAr2 ) . As seen in FIG . 11C , the 27 : 5601 - 18 ) . Due to these differences in stability between labile aryl halide of the DAPP having a reactive handle the alkyl - based versus aryl - based ions , different reaction ( II - 13 ) can be reacted with an aryl ether to append the ether pathways and different end - products can be observed . 35 by way of an SnAr2 reaction , thereby forming the further New strategies were required to effectively attach aryl - functionalized DAPP polymer ( II - 14 ) .

based functional groups on DAPP backbone and / or pendent groups . In particular , these developments included use of a Example 2 metal salt to promote aryl acylation . Effenberger published work discussing non - metal catalyzed , Friedel Crafts acy - 40 Acylation Using an Arylsulfonyl Reagent lation employing silver triflate ( see Effenberger F et al . , “ Trifluoromethanesulfonic - carboxylic anhydrides , highly FIG . 12 provides another exemplary reagent to provide a active acylation agents , ” Angew . Chem . Int ' l Ed . 1972 ; functionalized DAPP polymer . As described herein , the 11 ( 4 ) : 299 - 300 ) . Without wishing to be limited by mecha - reagent to provide the reactive handle can have the formula nism , a reaction between silver triflate and benzoyl chloride 45 RHX , in which RH can have the formula — LH — Ar or generally generates a trifluoromethanesulfonic - carboxylic LH - AKH ( e . g . , any described herein ) . In one instance , the anhydride and silver chloride ( FIG . 10C ) . The anhydride can exemplary RH — X reagent is Ar — LH - X , in which L " is then further react with arenes , such as benzene or a phenyl a sulfonyl and Art is an optionally substituted aryl . As seen ring to form benzophenone at high yields ( e . g . , a yield of in FIG . 12 , the RH — X agent includes a linker L? that is about 90 % or greater ) . One disadvantage of utilizing silver 50 sulfonyl ( 802 - ) and an aryl group And that is a fluori triflate in this manner is that for every aryl acyl chloride , at nated phenyl . least one equivalent of silver triflate is required . An alter - The reactive handle RH can be installed in any useful native to silver triflate , is employing triflic acid ; only a manner . In one instance , R? can be reacted with the F - la catalytic amount ( e . g . , 1 % ) can be used for the Friedel Crafts beled DAPP in the presence of a metal salt , e . g . , M ( OTf ) , a acylation of aryl acyl chlorides ( see , e . g . , Effenberger F et 55 metal triflate salt . The metal triflate can promote the Friedel al . , " Catalytic Friedel - Crafts acylation of aromatic com Crafts aryl acylation reaction , thereby providing an exem pounds , ” Angew . Chem . Int ' l Ed . 1972 ; 11 ( 4 ) : 300 - 1 ) . plary DAPP polymer ( II - 15 ) having one or more RH groups We have applied this chemistry onto a Diels - Alder poly - appended to the pendent aryl groups and / or the backbone

phenylene ( DAPP ) by reacting a F - labeled DAPP with aryl groups of the DAPP polymer . 4 - fluorobenzoyl chloride in the presence of sliver triflate 60 ( FIG . 11A ) , thereby producing a DAPP having one or more Example 3 reactive handles ( II - 13 ) . By using 19F - NMR and a fluorine in the polymer backbone as a reference , we can monitor the Synthesis of the Fluorinated Diels - Alder amount of trifluoromethylbenzoyl that is attached to the Poly ( Phenylene ) F - DAPP ( 3 * ) backbone ( see , e . g . , FIG . 11B ) . Any useful reaction condi - 65 tions can be modified to increase yield . For instance , reac - FIG . 13 provides the first step for a synthetic scheme , tion temperatures can be increased ( e . g . , of from about 60° which provides a fluorinated Diels - Alder poly ( phenylene )

US 10 , 053 , 534 B2 43 44

( II ) ( R ) ( R ) ( R ) ( R ) ( R ) ( R ) -

( R3 )

F - DAPP ( 3 * ) . To 16 . 9 g of bis ( teracyclone ) [ 24 . 5 mmol ] ( 1 * ) and 3 . 5 g of 1 , 4 diethyny - 2 - fluorobenzene [ 24 . 5 mmol ] ( 2 * ) in a 500 mL three neck round bottom flask was added 250 mL of diphenyl ether . The reaction vessel was heated to 5 165° C . under N2 . After 24 hours , the reaction vessel was cooled ; and the orange , viscous medium was precipitated from acetone . The solid was isolated , dried , and dissolved in toluene ( 10 mL of toluene per gram ) and then re - precipitated 10 from acetone . The resultant powder was isolated and dried in a vacuum oven at 150° C . for 48 hours , thereby providing F - labeled DAPP ( 3 * ) .

( R )

( R )

( R3 ) , X ( R ) L = L ( R34 , ( R ) ( R )

( R3 ) , ( R ' )

15

20

Example 4 or a salt thereof , wherein :

each R " is , independently , H , optionally substituted C1 - 12 Acylation of Diels - Alder Poly ( Phenylene ) alkyl , optionally substituted C1 - 12 haloalkyl , optionally Backbone with Silver Triflate substituted C1 - 12 perfluoroalkyl , optionally substituted

C1 - 12 heteroalkyl , halo , optionally substituted aryl , FIG . 13 also provides the second step for a synthetic optionally substituted alkaryl , optionally substituted

scheme , which provides a Diels - Alder poly ( phenylene ) hav arylalkoxy , optionally substituted aryloxy , optionally ing a reactive handle composed of a fluorinated acyl group 25 substituted aryloxycarbonyl , optionally substituted ary

loyl , optionally substituted arylcarbonylalkyl , option ( II - 16 ) . Under N , 2 g of the fluorinated Diels - Alder poly ally substituted arylsulfonyl , or optionally substituted ( phenylene ) ( 3 * ) [ 2 . 6 mmol ] was dissolved in 150 mL of arylsulfonylalkyl ; 1 , 2 - dichloroethane in a 500 mL three neck round bottom each Rl and R3 is , independently , H , halo , optionally flask . At room temperature , 2 . 4 g of 4 - fluorobenzoyl chlo - 30 substituted C1 - 12 alkyl , optionally substituted C1 - 12 ride [ 15 . 2 mmol ] and 3 . 9 g of AgOTf [ 15 . 2 mmol ] were haloalkyl , optionally substituted C1 - 12 perfluoroalkyl , added to the reaction vessel . The color of the solution optionally substituted C1 - 12 heteroalkyl , RS , RP , RC , or changed from an initial yellow solution to a dark red RF , wherein RS is an acidic moiety comprising a

sulfonyl group , R is an acidic moiety comprising a solution . The reaction was heated to 50° C . for 16 hours . The , phosphoryl group , R is an acidic moiety comprising a resultant slurry was filtered by passing through a 2 um glass carbonyl group , and R is an electron - withdrawing fiber syringe frit to remove excess AgoTfand AgCl . The red moiety ; solution was then precipitated from reagent ethanol and each Art is , independently , a bivalent linker comprising dried in a vacuum oven at 150° C . for 24 hours to provide optionally substituted arylene ;

40 each Ar is , independently , a bivalent linker comprising a fluoroacylated DAPP compound ( 11 - 16 ) . optionally substituted arylene ; Other Embodiments each q is , independently , an integer of from 0 to 5 ; All publications , patents , and patent applications men each h is , independently , an integer of from 0 to 5 ,

wherein at least one h is not 0 ; tioned in this specification are incorporated herein by ref - 45 m is an integer of from about 1 to 1000 : and erence to the same extent as if each independent publication wherein at least one RW on a pendent group of formula ( II ) or patent application was specifically and individually indi comprises a substituted aryl group comprising halo or cated to be incorporated by reference . alkoxy or aryloxy .

2 . The composition of claim 1 , wherein : While the invention has been described in connection 50 at least one RH is LH _ APH ;

with specific embodiments thereof , it will be understood that L " is a covalent bond , carbonyl , oxy , thio , azo , phospho it is capable of further modifications and this application is noyl , phosphoryl , sulfonyl , sulfinyl , sulfonamide , intended to cover any variations , uses , or adaptations of the imino , imine , phosphine , nitrilo , optionally substituted

C1 - 12 alkylene , optionally substituted C1 - 12 alkylene invention following , in general , the principles of the inven oxy , optionally substituted C1 - 12 heteroalkylene , tion and including such departures from the present disclo optionally substituted C1 - 12 heteroalkyleneoxy , option sure that come within known or customary practice within ally substituted C4 - 18 arylene , or optionally substituted the art to which the invention pertains and may be applied C4 - 18 aryleneoxy ; and to the essential features hereinbefore set forth , and follows ApH is an optionally substituted aryl .

60 3 . The composition of claim 2 , wherein LA is a covalent in the scope of the claims . bond , carbonyl , sulfonyl , NR23 — ( CRI Other embodiments are within the claims . R22 _ CIO NR23 — , - NR23C ( O ) - , - SO2 - NR23

- NR23 _ 3024 , ( CRLIR22 ) za C ( O ) - NR23 — , ( CRIR2 ) - NR23 _ C ( O ) - , ( CRLIR ? 2 ) za - S0 , The invention claimed is : 65 NR23 — , or S02 - NR23 ( CR IR ? ) a 1 . A composition comprising a structure having the for wherein each of R1 , R22 , and R23 is , independently , H ,

mula ( II ) : optionally substituted alkyl , optionally substituted

15

I

TH

20

( R3 ( Ra ( R3 ) . ( R )

( LH - ARH ) . 25

30 * ( K ) , am

US 10 , 053 , 534 B2 45 46

haloalkyl , optionally substituted alkoxy , optionally optionally substituted alkaryl ; each RS2 is , indepen substituted alkaryl , optionally substituted aryl , or halo ; dently , H , hydroxyl , optionally substituted alkyl , and optionally substituted alkylsulfonyl , optionally substi

wherein Art is optionally substituted with one or more tuted aryl , or optionally substituted alkaryl ; and each substituents selected from the group consisting of halo , 5 R $ 3 is , independently , H , hydroxyl , optionally substi cyano , optionally substituted haloalkyl , optionally sub tuted alkyl , optionally substituted C1 - 12 haloalkyl , stituted perfluoroalkyl , optionally substituted optionally substituted perfluoroalkyl , optionally substi nitroalkyl , and optionally substituted alkyl . tuted aryl , or optionally substituted alkaryl ;

4 . The composition of claim 1 , wherein the composition 1 . RP is — P ( O ) ( OH ) 2 or 0 - PO ( OH ) , or — P ( O ) < comprises a structure having the formula ( Ilk ) : RP ' RP2 or — P ( O ) < RARP2 or — P ( O ) < R4 ' R4r , and

wherein each of RP1 and RP2 is , independently , option ( IIK ) ally substituted alkyl , optionally substituted alkoxy ,

optionally substituted aryl , optionally substituted alkaryl , optionally substituted aryloxy , hydroxyl , or H ; and each of R4r is , independently , optionally substi tuted aryl , optionally substituted alkaryl , or optionally substituted aryloxy ;

RC isCO H , CORCI , or RC4 _ C ( O ) - RCI , and wherein each RCI is , independently , optionally substituted alkyl , optionally substituted alkoxy , option ally substituted aryl , optionally substituted alkaryl , optionally substituted aryloxy , hydroxyl , or H ; and each RCA is , independently , oxy , optionally substituted alky

( R ) lene , or optionally substituted heteroalkylene ; and R is optionally substituted aryloyl , carboxyaldehyde ,

30 optionally substituted alkanoyl , or optionally substi tuted alkyl .

8 . The composition of claim 1 , wherein Art and / or Amis optionally substituted phenylene , optionally substituted

as naphthylene , or optionally substituted phenanthrylene . 9 . The composition of claim 8 , wherein the optional

substitution for Art is RH , RS , RP , RC , or RF ; and wherein or a salt thereof , wherein : the optional substitution for ArM is RH , RS , RP , RC , RF , or Ly is a covalent bond , carbonyl , oxy , thio , azo , phospho - a label .

noyl , phosphoryl , sulfonyl , sulfinyl , sulfonamide , 40 40 10 . The composition of claim 1 , wherein the composition 1 imino , imine , phosphine , nitrilo , optionally substituted comprises a structure having formula ( IIj ) : C1 - 12 alkylene , optionally substituted C1 - 12 alkylene oxy , optionally substituted C1 - 12 heteroalkylene , optionally substituted C1 - 12 heteroalkyleneoxy , option ( IIj ) ally substituted C4 . 18 arylene , or optionally substituted 45 ( RH ) ( RH ) ( RH ) ( Rhine C4 - 18 aryleneoxy ; and

Art is an optionally substituted aryl . 5 . The composition of claim 1 , wherein at least one RH is

an optionally substituted C4 - 18 aryl , optionally substituted C1 - 6 alk - C4 - 18 aryl , optionally substituted C4 - 18 aryl - C1 - 6 50 alkoxy , optionally substituted C4 - 18 aryloxy , optionally sub stituted C5 - 19 aryloxycarbonyl , optionally substituted C5 - 19 aryloyl , optionally substituted C4 - 18 arylcarbonyl - C1 - 6 alkyl , optionally substituted C4 - 18 arylsulfonyl , or optionally sub stituted C4 - 18 arylsulfonyl - C1 - 6 alkyl ; and / or wherein at least 55 one RH is optionally substituted C4 - 18 aryloxy comprising one or more halo or haloalkyl .

6 . The composition of claim 5 , wherein each and every RH ( RH ) ( RM ) comprises a substituted aryl group . 7 . The composition of claim 1 , wherein : RS is - SO , RSI or S0 , - NRM _ RS2 or — SO2 - or a salt thereof , wherein : NRM _ 502 - RS3 , wherein each RSI is , independently , H , optionally substituted alkyl , optionally substituted each of Art and ATM is , independently , an optionally haloalkyl , optionally substituted perfluoroalkyl , option substituted phenylene . ally substituted aryl , optionally substituted alkaryl , or 65 11 . The composition of claim 1 , wherein the composition hydroxyl ; each RM is , independently , H or optionally comprises a structure having any one of formulas ( II - 1 ) to substituted C1 - 12 alkyl , optionally substituted aryl , or ( II - 10 ) and ( II - 13 ) to ( II - 18 ) :

Ar

m

60

US 10 , 053 , 534 B2 48

- continued ( II - 1 ) ( II - 3 )

RHI RH RH RA RHI

DO =

B Tacomo Oraco > 171

bit RH RH .

RHI RHU

8

8

8

( II - 4 ) ( II - 2 )

RHI RHI

8

SO3H 0 SOH

8

8

HOS

8

8

RHI RHI RAI

US 10 , 053 , 534 B2 49 50

- continued - continued ( II - 5 ) ( II - 8 )

RHI RHI RHI RHI RH

RH1 - RHI - RHI

10

20 17

m RHI DHI

pH | RHI RHI 25

RH RH1 ( II - 6 )

RH1 RH130 RH1RHI ( II - 9 )

[ RHI R # 1 RH F

RHI R # 1 so SO2 RH 35 F F F F

n SO2 RE RHI

RH1RH1

RH RH

RHI RHI ( II - 10 )

RHI F

217

US 10 , 053 , 534 B2 51 ) 52 51

- continued - continued ( II - 13 ) ( II - 15 )

F F F F

? ? SO , SO , SO

=

G

- EL g

- *

$ 0 ) $ 0 ) A f ?

g

g

g

5

( II - 14 ) ( II - 16 )

- OCHS 45

50

55

} OCH , 65

53 - continued

CF3

US 10 , 053 , 534 B2 54

optionally substituted C1 - 12 heteroalkyleneoxy , option ( II - 17 ) ally substituted C4 - 18 arylene , or optionally substituted

CF3 C4 - 18 aryleneoxy ; and Art is a substituted aryl .

5 13 . The composition of claim 12 , wherein the Art is a substituted phenyl .

14 . The composition of claim 12 , wherein the Art is an RH1 - substituted phenyl group , and wherein RM1 is selected from the group consisting of an amino , amido , azido , nitro , nitroso , haloalkyl , and halo .

15 . The composition of claim 12 , wherein LH is the covalent bond or carbonyl .

16 . The composition of claim 1 , wherein the composition 15 comprises a structure having formula ( Ili ) :

SO3H SO3H

( III ) ( RA ) - 111 ( RM )

20

( RH ) ( RA ) ( RM ) ( RA ) SO3H SO3H

and

( II - 18 ) 25 NMez NMe3 Ak Ak ÇF3

( RH ) 30 ApM7

Ak

m

35 ( RA ) ( RA ) ( RH )

40 or a salt thereof , wherein :

each of Art and ATM is , independently , an optionally substituted phenylene and

each and every RM comprises a substituted aryl group . 17 . The composition of claim 10 , wherein the composi

tion comprises a structure having formula ( Ilj ) : 45

( IIj ) CF3 Ak ( RH ) ( RA ) ( R ) ( R )

NMez 50 ? ? ? AR

or a salt thereof ; wherein : each RH1 is , independently , H , halo , cyano , optionally

substituted haloalkyl , optionally substituted perfluoro alkyl , optionally substituted nitroalkyl , or optionally 55 substituted alkyl ;

m is an integer of from about 1 to 500 ; each Ak is , independently , an optionally substituted alky

lene group ; and each hl is , independently , an integer of from 1 to 12 . 60 12 . The composition of claim 1 , wherein : at least one RH is LH Arh ; LH is a covalent bond , carbonyl , oxy , thio , azo , phospho noyl , phosphoryl , sulfonyl , sulfinyl , sulfonamide , imino , imine , phosphine , nitrilo , optionally substituted 65 C1 - 12 alkylene , optionally substituted C1 - 12 alkylene oxy , optionally substituted C1 - 12 heteroalkylene ,

- m

( RM ) ( R ) h

or a salt thereof , wherein : each of Art and ArM is , independently , an optionally

substituted phenylene and each and every RM comprises a substituted aryl group .

56

( III )

US 10 , 053 , 534 B2 55

18 . The composition of claim 4 , wherein each Art is substituted with one or more substituents selected from the group consisting of halo , cyano , optionally substituted haloalkyl , optionally substituted perfluoroalkyl , optionally 5 substituted nitroalkyl , and optionally substituted alkyl .

19 . The composition of claim 1 , wherein the composition comprises a structure having formula ( Ilq ) :

ARH

?? TH

10

( R ( Ilq )

RHI RHI - AKHI RHI RHI RHI

RHI ' Y RH R Y TH ( Rpla TH TH E

/ 20 H

AKH

( Rua R ' ) a TARH ( R ) 25

Ar .

( R ) ( R )

30 ( R ? ) ( R3 ) m

14 - RHI

35

RHIV RHI RH RHI

40

or a salt thereof , wherein : LH is a covalent bond , carbonyl , oxy , thio , azo , phospho

noyl , phosphoryl , sulfonyl , sulfinyl , sulfonamide , imino , imine , phosphine , nitrilo , optionally substituted 45 C1 - 12 alkylene , optionally substituted C1 - 12 alkylene oxy , optionally substituted C1 - 12 heteroalkylene , optionally substituted C1 - 12 heteroalkyleneoxy , option ally substituted C4 - 18 arylene , or optionally substituted so C4 - 18 aryleneoxy ; and

each RH1 is , independently , selected from the group con sisting of H , halo , cyano , amino , amido , azido , nitro , nitroso , optionally substituted haloalkyl , optionally 55 substituted perfluoroalkyl , optionally substituted nitroalkyl , optionally substituted aminoalkyl , option ally substituted aryloxy , and optionally substituted alkyl .

20 . The composition of claim 19 , wherein each R?l is , independently , selected from the group consisting of H , halo , optionally substituted haloalkyl , optionally substituted aminoalkyl , and optionally substituted aryloxy . 65

21 . A composition comprising a structure having the formula ( III ) :

or a salt thereof , wherein : L is a covalent bond , carbonyl , oxy , thio , azo , phospho

noyl , phosphoryl , sulfonyl , sulfinyl , sulfonamide , imino , imine , phosphine , nitrilo , optionally substituted C1 - 12 alkylene , optionally substituted C1 - 12 alkylene oxy , optionally substituted C1 - 12 heteroalkylene , optionally substituted C1 - 12 heteroalkyleneoxy , option ally substituted C4 - 18 arylene , or optionally substituted C4 - 18 aryleneoxy ;

AKH is a substituted alkyl or a substituted heteroalkyl , wherein each of the substituted alkyl or substituted heteroalkyl is substituted with one or more substituents selected from the group consisting of halo , cyano , amino , amido , azido , nitro , nitroso , optionally substi tuted haloalkyl , optionally substituted perfluoroalkyl , optionally substituted nitroalkyl , and optionally substi tuted alkyl ;

each R ' and R3 is , independently , H , halo , optionally substituted C1 - 12 alkyl , optionally substituted C1 - 12 haloalkyl , optionally substituted C1 - 12 perfluoroalkyl , optionally substituted C1 - 12 heteroalkyl , R " , RP , Rº , or R " , wherein RS is an acidic moiety comprising a sulfonyl group , RP is an acidic moiety comprising a phosphoryl group , R is an acidic moiety comprising a carbonyl group , and R is an electron - withdrawing moiety ;

each Art is , independently , a bivalent linker comprising optionally substituted arylene ;

each Am is , independently , a bivalent linker comprising optionally substituted arylene ;

each q is , independently , an integer of from 0 to 5 ; each h is , independently , an integer of from 0 to 5 , wherein at least one h is not 0 ; and

m is an integer of from about 1 to 1000 . 22 . The composition of claim 21 , wherein the composi

tion comprises a structure having formula ( IIr ) :

US 10 , 053 , 534 B2 57 57 58 58

( IIr ) ( II - 11 ) RHI R41 1

( RH1R Hl ] ni RHI RH1 — - RH ) 5 1 IV TH boost time 10

( R ? ( R ) , ( Kg ( R ) q

Ar

( R ' ) ml

( II - 12 ) Ryla am - 20 20

HF IRHRH RHI

25

or a salt thereof , wherein : each RH is , independently , selected from the group con

sisting of halo , cyano , amino , amido , azido , nitro , 30 nitroso , optionally substituted haloalkyl , optionally substituted perfluoroalkyl , optionally substituted nitroalkyl , and optionally substituted alkyl ; and

each hl is , independently , an integer of from 1 to 12 . 3 or a salt thereof , wherein : 23 . The composition of claim 21 , wherein the composi each hl is , independently , an integer of from 1 to 12 .

tion comprises a structure having formulas ( II - 11 ) or ( II - 12 ) :

7

* * * * *

Documents

MAI MULTE A MINHA CUI ON TO A M AN UNITI€¦ · Parcero E et al . , “ Phosphonated and sulfonated polyphenylsulfone membranes for fuel cell application , ” J . Membr . Sci